To develop more ideal bifunctional heteroatom-doped carbon electrocatalysts toward the oxygen reduction reaction (ORR) and oxygen evolution reaction (OER) for regenerative fuel cells and rechargeable metal–air batteries, herein, tobacco-derived N-containing ordered mesoporous carbon (N-OMC) electrocatalysts with different N species distributions are designed. Results indicate that the as-prepared N-OMC with more pyrrolic and pyridinic Ns exhibits much higher activities for the ORR and OER than N-OMC with more graphitic N in both acidic and alkaline media, suggesting that the increase of pyrrolic and pyridinic Ns favors the improvement of ORR and OER activities of the N-containing carbon catalysts, and showing a great potential for the designing of more effective, lower-cost ORR and OER bifunctional electrocatalysts for future regenerative fuel cells and rechargeable metal–air batteries.