Atomically　precise　thiolate-capped　metal　nanoclusters　(NCs),　as　a　recently　developed　category　of　metal　nanomaterials,　show　emerging　potential　in　solar　energy　harvesting　and　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　and　barren　active　sites　of　metal　NCs　as　well　as　instability　retard　the　photosensitization　efficiency　in　photoredox　catalysis.　Herein,　we　conceptually　demonstrate　the　general　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　a　ligand-initiated　self-assembly　route,　based　on　which　atomically　precise　metal　NCs　are　accurately　anchored　on　the　TMC　substrates　under　substantial　electrostatic　interaction.　It　was　unveiled　that　photoinduced　electrons　from　metal　NCs　can　flow　to　the　TMC　substrates　and　holes　migrate　in　an　opposite　direction,　featuring　the　quintessential　type　II　charge　transport　pathway　because　of　the　suitable　energy　level　alignment,　intimate　interfacial　integration　mode,　and　boosted　charge　separation.　Given　the　efficacious　interfacial　charge　migration/separation,　metal　NCs/TMC　heterostructures　exhibit　significantly　boosted　photoactivities　toward　selective　organic　transformation　and　solar-to-hydrogen　conversion　under　visible　light　irradiation.　Our　work　would　provide　new　insights　into　rationally　crafting　metal　NC-based　photosystems　and　open　a　promising　vista　for　modulating　vectorial　charge　transfer　over　metal　NCs　toward　substantial　solar-to-chemical　energy　conversion.　©　2022　American　Chemical　Society.　All　rights　reserved.