Atomically　precise　thiolate-capped　metal　nano-clusters　(NCs),　as　a　recently　developed　category　of　metalnanomaterials,　show　emerging　potential　in　solar　energy　harvestingand　conversion　owing　to　the　peculiar　atom-stacking　mode,quantum　confinement　effect,　and　discrete　energy　band　structure.However,　the　super-short　photoexcited　charge　carrier　life　span　andbarren　active　sites　of　metal　NCs　as　well　as　instability　retard　thephotosensitization　efficiency　in　photoredox　catalysis.　Herein,　weconceptually　demonstrate　thegeneral　design　of　glutathione(GSH)-capped　metal　NCs/transition　metal　chalcogenides(TMCs),　that　is,　metal　NCs　[Agx,Ag31(GSH)19,Ag16(GSH)9,Ag9(GSH)6]/TMC　(CdS,　Zn0.5Cd0.5S)　heterostructures　by　aligand-initiated　self-assembly　route,　based　on　which　atomically　precise　metal　NCs　are　accurately　anchored　on　the　TMC　substratesunder　substantial　electrostatic　interaction.　It　was　unveiled　that　photoinduced　electrons　from　metal　NCs　canflow　to　the　TMCsubstrates　and　holes　migrate　in　an　opposite　direction,　featuring　the　quintessential　type　II　charge　transport　pathway　because　of　thesuitable　energy　level　alignment,　intimate　interfacial　integration　mode,　and　boosted　charge　separation.　Given　the　efficacious　interfacialcharge　migration/separation,　metal　NCs/TMC　heterostructures　exhibit　significantly　boosted　photoactivities　toward　selective　organictransformation　and　solar-to-hydrogen　conversion　under　visible　light　irradiation.　Our　work　would　provide　new　insights　into　rationallycrafting　metal　NC-based　photosystems　and　open　a　promising　vista　for　modulating　vectorial　charge　transfer　over　metal　NCs　towardsubstantial　solar-to-chemical　energy　conversion.