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/H₂ 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.