While nitrogen (N)-doped carbon can facilitate the four-electron transfer in oxygen reduction reaction (ORR), its effect on the two-electron path is yet to be investigated. To date, the random N-C bond configurations in N-doped carbons make it difficult to identify the active sites for electrochemical reactions. Here, we report a preparation of well-controlled N-C configurations with high centrality as model catalysts for identification of active sites for two-electron transfer ORR. Specifically, the synthesized Pyrrolic-N doped single-wall carbon nanotube and graphene utilizing a microwave-assisted pulse heating method, exhibit excellent activity for two-electron path (H2O2 selectivity of 93.5% and 98.35%). X-ray adsorption near-edge structure spectroscopy measurements indicate that carbon atoms adjacent to Pyrrolic-N are the active sites for two-electron transfer. This work provides a viable way for the fabrication of tailored N configurations in carbon materials and significantly advances our understanding of the N moieties for the electrochemical H2O2 generation.