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. Atomically precise metal nanoclusters mediated Z‐scheme photosystems are for the first time exquisitely crafted for solar‐to‐hydrogen conversion. The favorable energy level alignment among Au25(GSH)18 nanoclusters, CdSe QDs, and MoSe2 along with elegant interface configuration modulation facilitates the directional charge migration and separation, giving rise to high‐performance Z‐scheme photosystem for photocatalytic hydrogen generation under visible light irradiation.