Pyridinic N is widely regarded as the active center while pyrrolic N has low-activity in metal-free N-doped carbon for electrocatalytic CO2 reduction reaction (CO2RR) to CO, but this viewpoint remains open to question. In this study, through density functional theoretical calculations, we first illustrate that the intrinsic activity of pyrrolic N is high enough for effectively catalyzing CO2RR, however, due to the interplay with the neighboring pyridinic N sites, the activity of pyrrolic N is dramatically suppressed. Then, experimentally, metal-free N-doped carbon spheres (NCS) electrocatalysts without significant pyridinic N content are prepared for CO2RR. The pyrrolic N in NCS shows a direct-positive correlation with the performance for CO2RR, representing the active center with high activity. The optimum NCS could produce syngas with a wide range of CO/H-2 ratio (0.09 to 12) in CO2RR depending on the applied potential, meanwhile, the best selectivity of 71% for CO can be obtained. Intentionally adding a small amount of pyridinic N to the optimum NCS dramatically decreases the activity for CO2RR, further verifying the suppressed activity of pyrrolic N sites by the neighboring pyridinic N sites. This work reveals the interaction between a variety of N species in N-doped carbon, and the potential of pyrrolic N as the new type of active site for electrocatalysts, which can improve our understanding of the electrocatalysis mechanism and be helpful for the rational design of high-efficient electrocatalysts.