Developing high‐efficiency and low‐cost photocatalysts by avoiding expensive noble metals, yet remarkably improving H2 evolution performance, is a great challenge. Noble‐metal‐free catalysts containing Co(Fe)NC moieties have been widely reported in recent years for electrochemical oxygen reduction reaction and have also gained noticeable interest for organic transformation. However, to date, no prior studies are available in the literature about the activity of N‐coordinated metal centers for photocatalytic H2 evolution. Herein, a new photocatalyst containing g‐C3N4 decorated with CoP nanodots constructed from low‐cost precursors is reported. It is for the first time revealed that the unique P(δ−)Co(δ+)N(δ−) surface bonding states lead to much superior H2 evolution activity (96.2 µmol h−1) compared to noble metal (Pt)‐decorated g‐C3N4 photocatalyst (32.3 µmol h−1). The quantum efficiency of 12.4% at 420 nm is also much higher than the record values (≈2%) of other transition metal cocatalysts‐loaded g‐C3N4. It is believed that this work marks an important step toward developing high‐performance and low‐cost photocatalytic materials for H2 evolution. The unique P(δ−)Co(δ+)N(δ−) surface bonding states are constructed by decorating crystalline CoP nanodots on the g‐C3N4 nanosheet, which results in a superior H2 evolution rate of 96.2 µmol h−1 with the highest quantum efficiency value of 12.4% at 420 nm.