<p>The Co–N–C catalyst has exhibited its effectiveness as a substitute for the 2e⁻ ORR in the synthesis of H₂O₂. However, it still exhibits low selectivity towards 2e⁻ ORR. In this work, the P doped Co–N–C (Co–N/P–C) electrocatalysts with enhanced performance for H₂O₂ production were synthesized through in situ P-doping method. Moreover, the P content of Co–N/P–C was varied to investigate its correlation with H₂O₂ selectivity. The results revealed that P doping greatly enhanced both selectivity and yield of H₂O₂. Under acidic conditions (pH = 1), Co–N/P–C-0.75 exhibited optimal 2e⁻ ORR performance (H₂O₂ yield of 174&#xa0;mmol&#xa0;g⁻¹&#xa0;h⁻¹, H₂O₂ selectivity of 34.39%, electron transfer (n) of 3.31), significantly outperforming the P-free Co–N–C catalyst (H₂O₂ yield of 64&#xa0;mmol&#xa0;g⁻¹&#xa0;h⁻¹, H₂O₂ selectivity of 10.81%, n of 3.78). Additionally, Co–N/P–C-0.75 based electron-Fenton process showed attractive performance for rhodamine B (RhB) degradation, whose degradation rate was two times higher than that of Co–N–C. The experimental findings revealed that the improved efficiency of Co–N/P–C-0.75 could be attributed to the substitution of coordinated N atom with less electronegative P atom, which enhanced the electron density around the Co atom and facilitated *OOH desorption for H₂O₂ production.</p> Graphical Abstract <p></p>