In summary, atomically dispersed AuKPCN materials have been developed that can simultaneously promote the photocatalytic formation of ·OH and H2O2, with apparent quantum efficiencies of more than 85% at 420 nm. Extensive experimental characterization and computational 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.