Atomically　precise　metal　nanoclusters　(NCs)　stand　out　within　metal　nanomaterials　due　to　the　distinctive　atomic　stacking　configuration,　discrete　energy　band,　quantum　confinement　effect,　and　enriched　catalytic　centers,　positioning　them　as　promising　substitutes　for　conventional　photosensitizers　in　solar　energy　absorption　and　utilization.　However,　the　light-induced　poor　stability　and　ultrashort　carrier　lifetime　of　metal　NCs　as　well　as　the　difficulties　in　modulating　charge　migration　collectively　constrain　their　potential　applications　in　photoredox　catalysis.　In　this　work,　we　conceptually　construct　the　metal　NC　artificial　photosystems　by　electrostatically　self-assembling　L-glutathione　(GSH)-capped　Au25(GSH)18　NCs　onto　transition　metal　chalcogenide　(TMC)　substrates　(CdS,　Zn0.5Cd0.5S,　and　ZnIn2S4)　at　ambient　conditions.　Benefiting　from　the　advantageous　photosensitization　effect　of　Au25@(GSH)18　NCs,　these　self-assembled　TMCs/　Au25@(GSH)18　NC　heterostructures　exhibit　significantly　enhanced　photocatalytic　hydrogen　production　performance　(λ　＞　420　nm).　This　universal　photoactivity　enhancement　is　predominantly　attributed　to　the　suitable　energy　level　alignment　between　Au25@(GSH)18　NCs　and　TMCs,　which　considerably　enhances　the　interfacial　charge　transfer　and　effectively　extends　the　carrier　lifetime.　In　addition,　the　photocatalytic　mechanism　is　determined.　This　work　would　spark　continued　interest　in　crafting　diverse　atomically　precise　metal　NC　photocatalytic　systems　toward　solar-to-hydrogen　energy　conversion.　©　2025　American　Chemical　Society.