Atomically　precise　metal　nanoclusters　(NCs),　distinguished　by　their　unique　electronic　structures,　quantum　confinement　effects,　and　enriched　active　sites,　have　been　considered　highly　promising　photosensitizers　for　light　harvesting　and　conversion.　However,　the　ultra-short　carrier　lifetime　and　poor　stability　of　metal　NCs　remarkably　retard　their　widespread　applications　in　photocatalysis.　In　this　study,　we　achieved　the　modulation　of　carrier　separation　over　metal　NCs　via　heterostructure　engineering　by　smartly　integrating　atomically　precise　silver　NCs　[Ag16(GSH)9]　with　transition　metal　chalcogenides　(TMCs).　The　favorable　energy　level　alignment　between　metal　NCs　and　TMCs　facilitates　the　electron　transfer　from　the　metal　NCs　to　the　TMCs,　leading　to　a　significantly　prolonged　charge　lifetime　and　considerably　enhanced　photoactivity　toward　the　selective　reduction　of　nitro　compounds　to　amino　derivatives　under　visible　light.　The　photocatalytic　mechanism　of　these　composite　photosystems　is　elucidated　herein.　This　work　advances　our　fundamental　understanding　of　charge　transfer　mechanisms　over　atomically　precise　metal　NCs　for　solar　energy　conversion.　©　2024　The　Royal　Society　of　Chemistry.