Nitrogen-doped carbon materials (NCs) are extensively studied for the oxygen reduction reaction (ORR). However, the nature of active sites of pyridinic nitrogen (N_P) or graphitic nitrogen (N_G) on NCs is still under debate. Herein, we demonstrated that the ORR activity of NCs in alkaline media depended on the electronic synergism between N_P and N_G, rather than any single type of N. We measured the transferable electrons of NCs by absorption spectroscopy using 7′7′8′8-tetracyanoquinodimethane as an electron acceptor. The transferable electron amount of NCs is relevant to either N_P or N_G, leading to the [N_P] : [N_G] ratio as an electron transfer descriptor of NCs in a reverse volcano curve manner across nineteen NCs. The similar dependence of ORR activity on the [N_P] : [N_G] ratio of NCs was also discovered, demonstrating the synergistic effect of N_P and N_G. These results provide a new angle to understand the nature of ORR activity of NCs and optimize the ORR catalyst.