In summary, atomically dispersed AuKPCN materials that can simultaneously promote the photocatalytic formation of ⋅OH and H₂O₂ have been developed, with apparent quantum efficiencies of more than 85% at 420 nm. Extensive experimental characterization and computa tional simulations have shown that the atomically dispersed Au with low oxidation number alters the band structure of the material to capture the highly localized holes created under light excitation. This study effectively overcomes the common challenge of slow kinetics of conventional 4e^- WOR/2e^- WOR process, and it is poised to serve as a significant milestone to inspire researchers in the field of photocatalytic water purification.