Herein,　we　explore　a　general　Cu2−xS　nanocube　template-assisted　and　reverse　cation　exchange-mediated　growth　strategy　for　fabricating　hollow　multinary　metal　sulfide.　Unlike　the　traditional　cation　exchange　method　controlled　by　the　metal　sulfide　constant,　the　introduction　of　tri-n-butylphosphine　(TBP)　can　reverse　cation　exchange　to　give　a　series　of　hollow　metal　sulfides.　A　variety　of　hollow　multinary　metal　sulfide　cubic　nanostructures　has　been　demonstrated　while　preserving　anisotropic　shapes　to　the　as-synthesized　templates,　including　binary　compounds　(CdS,　ZnS,　Ag2S,　PbS,　SnS),　ternary　compound　(CuInS2,　ZnxCd1−xS),　and　quaternary　compound　(single-atom　platinum　anchored　ZnxCd1−xS;　ZnxCd1−xS-Pt1).　Experimental　and　density　functional　theory　(DFT)　calculations　show　that　the　hollow　metal　sulfide　semiconductors　obtained　could　significantly　improve　the　separation　and　migration　of　photogenerated　electron-hole　pairs.　Owing　to　the　efficient　charge　transfer,　the　ZnxCd1−xS-Pt1　exhibited　outstanding　photocatalytic　performance　of　CO2　to　CO,　with　the　highest　CO　generation　rate　of　75.31　μmol　h−1.　©　2021　Wiley-VCH　GmbH