AbstractThe local atomic environments of single‐atom photocatalysts play a decisive role in determining the solar‐to‐hydrogen energy conversion efficiency. However, controllably modulating the microstructure of single‐atom sites to enhance catalytic activity and deeply understanding the structure‐property relationship remain great challenges. Herein, electron‐rich P atoms are introduced to accurately regulate the local coordination environment and electronic configuration of Fe single atoms and construct a unique asymmetrical FeN3P2 motif into carbon nitride (FeN3P2‐CN) for significantly improving the photocatalytic H2 evolution activity and stability. Specifically, in the absence of noble metal cocatalyst and photosensitizer, the FeN3P2‐CN achieves a remarkable H2 evolution rate of 2668.5 µmol g−1 h−1 under visible light irradiation (λ > 420 nm), more than 105 times higher than that of unregulated FeN4 sample. Systematic characterizations and theoretical calculations unveil that the FeN3P2 single‐atom sites not only significantly broaden the photoabsorption region and facilitate the charge separation and interfacial transfer, but also efficiently promote adsorption and activation of H2O. This work paves a promising pathway to design novel single‐atom photocatalysts at the atomic level for achieving highly efficient water‐splitting performance.