<?xml version="1.0" encoding="us-ascii"?>
<!--XBRL document created by DFIN IXG 1.0.0.0 using Fujitsu Interstage XWand-->
<schema targetNamespace="http://www.vanguard.com/20240226" elementFormDefault="qualified" xmlns="http://www.w3.org/2001/XMLSchema" xmlns:star="http://www.vanguard.com/20240226" xmlns:xlink="http://www.w3.org/1999/xlink" xmlns:link="http://www.xbrl.org/2003/linkbase" xmlns:xbrli="http://www.xbrl.org/2003/instance" xmlns:dtr-types="http://www.xbrl.org/dtr/type/2022-03-31" xmlns:rr="http://xbrl.sec.gov/rr/2023">
  <annotation>
    <appinfo>
      <link:linkbaseRef xlink:type="simple" xlink:href="star-20240226_pre.xml" xlink:title="Presentation Links, all" xlink:role="http://www.xbrl.org/2003/role/presentationLinkbaseRef" xlink:arcrole="http://www.w3.org/1999/xlink/properties/linkbase" />
      <link:linkbaseRef xlink:type="simple" xlink:href="star-20240226_cal.xml" xlink:title="Calculation Links, all" xlink:role="http://www.xbrl.org/2003/role/calculationLinkbaseRef" xlink:arcrole="http://www.w3.org/1999/xlink/properties/linkbase" />
      <link:linkbaseRef xlink:type="simple" xlink:href="star-20240226_def.xml" xlink:title="Definition Links, all" xlink:role="http://www.xbrl.org/2003/role/definitionLinkbaseRef" xlink:arcrole="http://www.w3.org/1999/xlink/properties/linkbase" />
      <link:linkbaseRef xlink:type="simple" xlink:href="star-20240226_lab.xml" xlink:title="Label Links, all" xlink:role="http://www.xbrl.org/2003/role/labelLinkbaseRef" xlink:arcrole="http://www.w3.org/1999/xlink/properties/linkbase" />
      <link:roleType roleURI="http://www.vanguard.com/role/DocumentDocumentandEntityInformationElements" id="httpwwwvanguardcomroleDocumentDocumentandEntityInformationElements">
        <link:definition>000000 - Document - Document and Entity Information {Elements}</link:definition>
        <link:usedOn>link:presentationLink</link:usedOn>
        <link:usedOn>link:calculationLink</link:usedOn>
        <link:usedOn>link:definitionLink</link:usedOn>
      </link:roleType>
      <link:roleType roleURI="http://www.vanguard.com/role/ScheduleAnnualFundOperatingExpenses000013" id="httpwwwvanguardcomroleScheduleAnnualFundOperatingExpenses000013">
        <link:definition>000013 - Schedule - Annual Fund Operating Expenses</link:definition>
        <link:usedOn>link:calculationLink</link:usedOn>
        <link:usedOn>link:presentationLink</link:usedOn>
        <link:usedOn>link:definitionLink</link:usedOn>
      </link:roleType>
      <link:roleType roleURI="http://www.vanguard.com/role/DisclosureRiskReturnDetailDataElementsVanguardLifeStrategyIncomeFundRetail" id="httpwwwvanguardcomroleDisclosureRiskReturnDetailDataElementsVanguardLifeStrategyIncomeFundRetail">
        <link:definition>000019 - Disclosure - Risk/Return Detail Data {Elements} - Vanguard LifeStrategy Income Fund (Retail)</link:definition>
        <link:usedOn>link:presentationLink</link:usedOn>
        <link:usedOn>link:calculationLink</link:usedOn>
        <link:usedOn>link:definitionLink</link:usedOn>
      </link:roleType>
      <link:roleType roleURI="http://www.vanguard.com/role/DisclosureRiskReturnDetailDataElementsVanguardLifeStrategyConservativeGrowthFundRetail" id="httpwwwvanguardcomroleDisclosureRiskReturnDetailDataElementsVanguardLifeStrategyConservativeGrowthFundRetail">
        <link:definition>000029 - Disclosure - Risk/Return Detail Data {Elements} - Vanguard LifeStrategy Conservative Growth Fund (Retail)</link:definition>
        <link:usedOn>link:presentationLink</link:usedOn>
        <link:usedOn>link:calculationLink</link:usedOn>
        <link:usedOn>link:definitionLink</link:usedOn>
      </link:roleType>
      <link:roleType roleURI="http://www.vanguard.com/role/DisclosureRiskReturnDetailDataElementsVanguardLifeStrategyModerateGrowthFundRetail" id="httpwwwvanguardcomroleDisclosureRiskReturnDetailDataElementsVanguardLifeStrategyModerateGrowthFundRetail">
        <link:definition>000039 - Disclosure - Risk/Return Detail Data {Elements} - Vanguard LifeStrategy Moderate Growth Fund (Retail)</link:definition>
        <link:usedOn>link:presentationLink</link:usedOn>
        <link:usedOn>link:calculationLink</link:usedOn>
        <link:usedOn>link:definitionLink</link:usedOn>
      </link:roleType>
      <link:roleType roleURI="http://www.vanguard.com/role/DisclosureRiskReturnDetailDataElementsVanguardLifeStrategyGrowthFundRetail" id="httpwwwvanguardcomroleDisclosureRiskReturnDetailDataElementsVanguardLifeStrategyGrowthFundRetail">
        <link:definition>000049 - Disclosure - Risk/Return Detail Data {Elements} - Vanguard LifeStrategy Growth Fund (Retail)</link:definition>
        <link:usedOn>link:presentationLink</link:usedOn>
        <link:usedOn>link:calculationLink</link:usedOn>
        <link:usedOn>link:definitionLink</link:usedOn>
      </link:roleType>
      <link:roleType roleURI="http://www.vanguard.com/role/DisclosureRiskReturnDetailDataElementsVanguardSTARFundRetail" id="httpwwwvanguardcomroleDisclosureRiskReturnDetailDataElementsVanguardSTARFundRetail">
        <link:definition>000059 - Disclosure - Risk/Return Detail Data {Elements} - Vanguard STAR Fund (Retail)</link:definition>
        <link:usedOn>link:presentationLink</link:usedOn>
        <link:usedOn>link:calculationLink</link:usedOn>
        <link:usedOn>link:definitionLink</link:usedOn>
      </link:roleType>
      <link:roleType roleURI="http://www.vanguard.com/role/DisclosureRiskReturnDetailDataElementsVanguardTotalInternationalStockIndexFundInvestor" id="httpwwwvanguardcomroleDisclosureRiskReturnDetailDataElementsVanguardTotalInternationalStockIndexFundInvestor">
        <link:definition>000069 - Disclosure - Risk/Return Detail Data {Elements} - Vanguard Total International Stock Index Fund (Investor)</link:definition>
        <link:usedOn>link:presentationLink</link:usedOn>
        <link:usedOn>link:calculationLink</link:usedOn>
        <link:usedOn>link:definitionLink</link:usedOn>
      </link:roleType>
      <link:roleType roleURI="http://www.vanguard.com/role/DisclosureRiskReturnDetailDataElementsVanguardTotalInternationalStockIndexFundAdmiral" id="httpwwwvanguardcomroleDisclosureRiskReturnDetailDataElementsVanguardTotalInternationalStockIndexFundAdmiral">
        <link:definition>000079 - Disclosure - Risk/Return Detail Data {Elements} - Vanguard Total International Stock Index Fund (Admiral)</link:definition>
        <link:usedOn>link:presentationLink</link:usedOn>
        <link:usedOn>link:calculationLink</link:usedOn>
        <link:usedOn>link:definitionLink</link:usedOn>
      </link:roleType>
      <link:roleType roleURI="http://www.vanguard.com/role/DisclosureRiskReturnDetailDataElementsVanguardTotalInternationalStockIndexFundETF" id="httpwwwvanguardcomroleDisclosureRiskReturnDetailDataElementsVanguardTotalInternationalStockIndexFundETF">
        <link:definition>000089 - Disclosure - Risk/Return Detail Data {Elements} - Vanguard Total International Stock Index Fund (ETF)</link:definition>
        <link:usedOn>link:presentationLink</link:usedOn>
        <link:usedOn>link:calculationLink</link:usedOn>
        <link:usedOn>link:definitionLink</link:usedOn>
      </link:roleType>
      <link:roleType roleURI="http://www.vanguard.com/role/DisclosureRiskReturnDetailDataElementsVanguardTotalInternationalStockIndexFundInstitutional" id="httpwwwvanguardcomroleDisclosureRiskReturnDetailDataElementsVanguardTotalInternationalStockIndexFundInstitutional">
        <link:definition>000099 - Disclosure - Risk/Return Detail Data {Elements} - Vanguard Total International Stock Index Fund (Institutional)</link:definition>
        <link:usedOn>link:presentationLink</link:usedOn>
        <link:usedOn>link:calculationLink</link:usedOn>
        <link:usedOn>link:definitionLink</link:usedOn>
      </link:roleType>
      <link:roleType roleURI="http://www.vanguard.com/role/DisclosureRiskReturnDetailDataElementsVanguardTotalInternationalStockIndexFundInstitutionalSelect" id="httpwwwvanguardcomroleDisclosureRiskReturnDetailDataElementsVanguardTotalInternationalStockIndexFundInstitutionalSelect">
        <link:definition>000109 - Disclosure - Risk/Return Detail Data {Elements} - Vanguard Total International Stock Index Fund (Institutional Select)</link:definition>
        <link:usedOn>link:presentationLink</link:usedOn>
        <link:usedOn>link:calculationLink</link:usedOn>
        <link:usedOn>link:definitionLink</link:usedOn>
      </link:roleType>
    </appinfo>
  </annotation>
  <import namespace="http://www.xbrl.org/2003/instance" schemaLocation="http://www.xbrl.org/2003/xbrl-instance-2003-12-31.xsd" />
  <import namespace="http://www.xbrl.org/2003/linkbase" schemaLocation="http://www.xbrl.org/2003/xbrl-linkbase-2003-12-31.xsd" />
  <import namespace="http://xbrl.sec.gov/rr/2023" schemaLocation="https://xbrl.sec.gov/rr/2023/rr-2023.xsd" />
  <import namespace="http://xbrl.sec.gov/dei/2023" schemaLocation="https://xbrl.sec.gov/dei/2023/dei-2023.xsd" />
  <import namespace="http://www.xbrl.org/dtr/type/2022-03-31" schemaLocation="https://www.xbrl.org/dtr/type/2022-03-31/types.xsd" />
  <element name="RetailMember" id="star_RetailMember" type="dtr-types:domainItemType" substitutionGroup="xbrli:item" abstract="false" nillable="true" xbrli:periodType="duration" />
  <element name="S000002929Member" id="star_S000002929Member" type="dtr-types:domainItemType" substitutionGroup="xbrli:item" abstract="false" nillable="true" xbrli:periodType="duration" />
  <element name="ReturnAfterTaxesonDistributionsMember" id="star_ReturnAfterTaxesonDistributionsMember" type="dtr-types:domainItemType" substitutionGroup="xbrli:item" abstract="false" nillable="true" xbrli:periodType="duration" />
  <element name="ReturnAfterTaxesonDistributionsandSaleofFundSharesMember" id="star_ReturnAfterTaxesonDistributionsandSaleofFundSharesMember" type="dtr-types:domainItemType" substitutionGroup="xbrli:item" abstract="false" nillable="true" xbrli:periodType="duration" />
  <element name="IncomeCompositeIndexMember" id="star_IncomeCompositeIndexMember" type="dtr-types:domainItemType" substitutionGroup="xbrli:item" abstract="false" nillable="true" xbrli:periodType="duration" />
  <element name="BloombergUSAggregateBondIndexMember" id="star_BloombergUSAggregateBondIndexMember" type="dtr-types:domainItemType" substitutionGroup="xbrli:item" abstract="false" nillable="true" xbrli:periodType="duration" />
  <element name="C000008017Member" id="star_C000008017Member" type="dtr-types:domainItemType" substitutionGroup="xbrli:item" abstract="false" nillable="true" xbrli:periodType="duration" />
  <element name="S000002927Member" id="star_S000002927Member" type="dtr-types:domainItemType" substitutionGroup="xbrli:item" abstract="false" nillable="true" xbrli:periodType="duration" />
  <element name="ConservativeGrowthCompositeIndexMember" id="star_ConservativeGrowthCompositeIndexMember" type="dtr-types:domainItemType" substitutionGroup="xbrli:item" abstract="false" nillable="true" xbrli:periodType="duration" />
  <element name="DowJonesUSTotalStockMarketFloatAdjustedIndexMember" id="star_DowJonesUSTotalStockMarketFloatAdjustedIndexMember" type="dtr-types:domainItemType" substitutionGroup="xbrli:item" abstract="false" nillable="true" xbrli:periodType="duration" />
  <element name="C000008015Member" id="star_C000008015Member" type="dtr-types:domainItemType" substitutionGroup="xbrli:item" abstract="false" nillable="true" xbrli:periodType="duration" />
  <element name="S000002930Member" id="star_S000002930Member" type="dtr-types:domainItemType" substitutionGroup="xbrli:item" abstract="false" nillable="true" xbrli:periodType="duration" />
  <element name="ModerateGrowthCompositeIndexMember" id="star_ModerateGrowthCompositeIndexMember" type="dtr-types:domainItemType" substitutionGroup="xbrli:item" abstract="false" nillable="true" xbrli:periodType="duration" />
  <element name="C000008018Member" id="star_C000008018Member" type="dtr-types:domainItemType" substitutionGroup="xbrli:item" abstract="false" nillable="true" xbrli:periodType="duration" />
  <element name="S000002928Member" id="star_S000002928Member" type="dtr-types:domainItemType" substitutionGroup="xbrli:item" abstract="false" nillable="true" xbrli:periodType="duration" />
  <element name="GrowthCompositeIndexMember" id="star_GrowthCompositeIndexMember" type="dtr-types:domainItemType" substitutionGroup="xbrli:item" abstract="false" nillable="true" xbrli:periodType="duration" />
  <element name="C000008016Member" id="star_C000008016Member" type="dtr-types:domainItemType" substitutionGroup="xbrli:item" abstract="false" nillable="true" xbrli:periodType="duration" />
  <element name="S000002931Member" id="star_S000002931Member" type="dtr-types:domainItemType" substitutionGroup="xbrli:item" abstract="false" nillable="true" xbrli:periodType="duration" />
  <element name="STARCompositeIndexMember" id="star_STARCompositeIndexMember" type="dtr-types:domainItemType" substitutionGroup="xbrli:item" abstract="false" nillable="true" xbrli:periodType="duration" />
  <element name="STARCompositeAverageMember" id="star_STARCompositeAverageMember" type="dtr-types:domainItemType" substitutionGroup="xbrli:item" abstract="false" nillable="true" xbrli:periodType="duration" />
  <element name="C000008019Member" id="star_C000008019Member" type="dtr-types:domainItemType" substitutionGroup="xbrli:item" abstract="false" nillable="true" xbrli:periodType="duration" />
  <element name="InvestorMember" id="star_InvestorMember" type="dtr-types:domainItemType" substitutionGroup="xbrli:item" abstract="false" nillable="true" xbrli:periodType="duration" />
  <element name="S000002932Member" id="star_S000002932Member" type="dtr-types:domainItemType" substitutionGroup="xbrli:item" abstract="false" nillable="true" xbrli:periodType="duration" />
  <element name="FTSEGlobalAllCapexUSIndexMember" id="star_FTSEGlobalAllCapexUSIndexMember" type="dtr-types:domainItemType" substitutionGroup="xbrli:item" abstract="false" nillable="true" xbrli:periodType="duration" />
  <element name="C000008020Member" id="star_C000008020Member" type="dtr-types:domainItemType" substitutionGroup="xbrli:item" abstract="false" nillable="true" xbrli:periodType="duration" />
  <element name="AdmiralMember" id="star_AdmiralMember" type="dtr-types:domainItemType" substitutionGroup="xbrli:item" abstract="false" nillable="true" xbrli:periodType="duration" />
  <element name="C000094037Member" id="star_C000094037Member" type="dtr-types:domainItemType" substitutionGroup="xbrli:item" abstract="false" nillable="true" xbrli:periodType="duration" />
  <element name="ETFMember" id="star_ETFMember" type="dtr-types:domainItemType" substitutionGroup="xbrli:item" abstract="false" nillable="true" xbrli:periodType="duration" />
  <element name="BasedonNAVMember" id="star_BasedonNAVMember" type="dtr-types:domainItemType" substitutionGroup="xbrli:item" abstract="false" nillable="true" xbrli:periodType="duration" />
  <element name="BasedonMarketPriceMember" id="star_BasedonMarketPriceMember" type="dtr-types:domainItemType" substitutionGroup="xbrli:item" abstract="false" nillable="true" xbrli:periodType="duration" />
  <element name="C000094038Member" id="star_C000094038Member" type="dtr-types:domainItemType" substitutionGroup="xbrli:item" abstract="false" nillable="true" xbrli:periodType="duration" />
  <element name="TransactionFeeOnPurchasesandSales" id="star_TransactionFeeOnPurchasesandSales" type="rr:NonNegativeMonetaryType" substitutionGroup="xbrli:item" abstract="false" nillable="true" xbrli:periodType="duration" />
  <element name="TransactionFeeOnReinvestedDividends" id="star_TransactionFeeOnReinvestedDividends" type="rr:NonNegativeMonetaryType" substitutionGroup="xbrli:item" abstract="false" nillable="true" xbrli:periodType="duration" />
  <element name="TransactionFeeOnConversionToETFShares" id="star_TransactionFeeOnConversionToETFShares" type="rr:NonNegativeMonetaryType" substitutionGroup="xbrli:item" abstract="false" nillable="true" xbrli:periodType="duration" />
  <element name="InstitutionalMember" id="star_InstitutionalMember" type="dtr-types:domainItemType" substitutionGroup="xbrli:item" abstract="false" nillable="true" xbrli:periodType="duration" />
  <element name="C000094036Member" id="star_C000094036Member" type="dtr-types:domainItemType" substitutionGroup="xbrli:item" abstract="false" nillable="true" xbrli:periodType="duration" />
  <element name="C000094039Member" id="star_C000094039Member" type="dtr-types:domainItemType" substitutionGroup="xbrli:item" abstract="false" nillable="true" xbrli:periodType="duration" />
  <element name="InstitutionalSelectMember" id="star_InstitutionalSelectMember" type="dtr-types:domainItemType" substitutionGroup="xbrli:item" abstract="false" nillable="true" xbrli:periodType="duration" />
  <element name="C000170278Member" id="star_C000170278Member" type="dtr-types:domainItemType" substitutionGroup="xbrli:item" abstract="false" nillable="true" xbrli:periodType="duration" />
</schema>
