Metal　nanoclusters　(NCs),　characterized　by　the　merits　of　unique　stacking　structure,　quantum　confinement　effect,　and　abundant　active　centers,　have　garnered　enormous　attention　in　photocatalysis.　However,　inherent　instability,　fast　carrier　recombination,　and　complex　interfacial　charge　transport　mechanism　of　metal　NCs　remain　the　core　challenges,　thereby　refraining　their　wide-spread　applications　in　heterogeneous　photocatalysis.　In　this　work,　tailor-made　L-glutathione　reduced　(GSH)　protected　Au22(GSH)18　NCs　are　anchored　on　the　transition　metal　chalcogenide　(CdS)　for　constructing　CdS/Au22(GSH)18　heterostructure　artificial　photosystems　by　a　self-assembly　approach.　The　CdS/Au22(GSH)18　nanocomposite　exhibits　the　improved　visible-light-driven　photoactivity　for　reduction　of　aromatic　nitro　compounds　compared　with　single　counterpart.　This　is　mainly　attributed　to　the　pivotal　role　of　Au22(GSH)18　NCs　as　visible-light-absorbing　antennas　and　the　suitable　energy　level　alignment　between　Au22(GSH)18　NCs　and　CdS,　considerably　improving　the　charge　migration　and　separation　efficiency　and　thereby　enhancing　the　photocatalytic　performances.　Our　investigation　provides　enriched　information　on　the　charge　transport　mechanism　of　metal　NCs　in　photoredox　organic　transformation.　©　2025　Elsevier　B.V.