Metal　nanoclusters　(NCs)　have　been　deemed　as　a　promising　photosensitizers　for　solar　energy　conversion　given　their　discrete　energy　band　structure,　unique　atom-stacking　fashion　and　enriched　active　centers.　However,　constructing　high-efficiency　metal　NCs-based　photocatalytic　systems　has　still　been　lacking　because　of　the　incompatible　energy　level　between　metal　NCs　with　semiconductors.　In　this　work,　we　demonstrate　the　rational　design　of　metal　NCs/transition　metal　chalcogenides　heterostructure　photosystem　via　a　facile　electrostatic　self-assembly,　wherein　Aux@GSH　NCs　(GSH:　glutathione)　are　precisely　anchored　on　the　CdS　nanowires　(NWs)　and　act　as　efficient　photosensitizers.　The　advantageous　charge　transport　between　CdS　NWs　and　Aux@GSH　NCs　triggered　by　favorable　energy　level　configuration　gives　rise　to　the　considerably　boosted　charge　separation　efficiency.　The　resultant　Aux　NCs/　CdS　heterostructures　exhibit　the　significantly　improved　photoredox　performances　towards　photocatalytic　organic　transformation,　mineralization　of　organic　pollutants,　and　heavy　metal　ion　(Cr6+)　reduction　under　visible　light.　This　work　offers　a　new　ideal　for　crafting　metal　NCs-based　artificial　photosystems　with　multi-functional　photocatalytic　applications.