Photocatalytic　H2evolution　and　biomass-derived　alcohol　oxidation　is　a　cooperative　way　for　improving　the　utilization　of　photogenerated　charge　carriers.　Herein,　a　highly　efficient　photocatalyst　was　fabricated　by　decorating　Zn0.5Cd0.5S　with　a　C,N　codoped　CoP　polyhedron　(referred　to　as　CoP,　derived　from　ZIF-67),　and　then　it　was　used　for　H2evolution　and　5-hydroxymethylfurfural　(HMF)　oxidation.　For　the　optimized　sample　(20%　CoP/Zn0.5Cd0.5S),　the　generated　H2rate　is　significantly　enhanced　from　that　of　the　HMF　aqueous　solution　with　2,5-diformylfuran　(DFF)　as　a　concomitant　product,　about　31.7　times　higher　than　the　pristine　Zn0.5Cd0.5S　under　visible　light　irradiation.　The　separation　of　photoexcited　electrons　(e-)　and　holes　(h+)　in　the　process　was　promoted,　as　both　e-and　h+were　involved　in　the　desired　conversions.　From　the　results　of　density　functional　theory　(DFT)　calculations　and　in　situ　XPS　spectra,　the　utilization　of　e-was　further　improved　as　a　spontaneous　transfer　from　Zn0.5Cd0.5S　to　CoP　occurred　due　to　the　p-n　heterojunction　formed　between　Zn0.5Cd0.5S　(n　type)　and　CoP　(p　type).　This　work　provides　an　efficient　method　to　separate　the　photoinduced　charge　carriers　and　a　new　way　for　H2evolution　accompanied　by　transformation　of　HMF　to　DFF.　©　2022　American　Chemical　Society.　All　rights　reserved.