Atomically　precise　metal　nanoclusters　(NCs)　represent　a　promising　generation　of　metal　nanomaterial　because　of　characteristic　atomic　stacking　mode,　abundant　catalytic　active　sites,　and　molecular-like　discrete　energy　band　structure.　However,　crafting　metal　NCs-dominated　photocatalytic　systems　with　mediated　charge　transport　pathways　for　photoredox　catalysis　is　in　the　infant　stage　and　their　photocatalytic　mechanisms　remain　elusive,　which　is　largely　hampered　by　the　ultra-short　charge　lifetime,　generic　instability,　and　complicated　electronic　structure　of　metal　NCs.　In　this　study,　the　smart　construction　of　all-solid-state　metal　NCs-transition　metal　chalcogenides　quantum　dots　(TMCs　QDs)　Z-scheme　artificial　photosystems　for　robust　and　stable　solar-to-hydrogen　conversion　is　demonstrated.　The　concurrent　favorable　photosensitization　efficiency　of　metal　NCs　and　TMCs　QDs　synergistically　stimulate　the　unexpected　Z-scheme　charge　transport　pathway,　which　significantly　boosts　the　anisotropic　spatial　vectorial　charge　transport/separation,　giving　rise　to　considerably　enhanced　visible-light-responsive　photocatalytic　hydrogen　generation　performances　along　with　favorable　stability.　This　study　would　push　forward　the　prosperity　of　exploring　metal　NCs-based　photosystems　for　solar-to-hydrogen　conversion.　©　2023　Wiley-VCH　GmbH.