To replace high-cost platinum group metal (PGM) electrocatalysts for oxygen reduction reaction (ORR) that is the crucial cathode reaction in fuel cell technology and metal-air battery, the development of low-cost and high-efficiency non-PGM catalysts for ORR has attracted much attention during the past decades. As one of the promising candidates, N-doped carbon is highly desirable for its strong designability and outstanding catalytic activity and stability. In this work, a facile and rational strategy is demonstrated for preparation of N,P-codoped mesoporous carbon (N,P-MC) for ORR by the direct pyrolysis treatment of polypyrrole with phytic acid as P-dopant and polystyrene sphere as template. The resultant N,P-MC exhibits a mesoporous structure with the optimized ORR active sites originating from the N,P-codoping. Owing to these features, N,P-MC exhibits excellent ORR activity, remarkable electrochemical stability, and superior methanol tolerance, comparable or even better than that of commercial Pt/C catalyst. The origin of enhanced ORR performance can be attributed to both the increased active sites and the mesoporous structure, which is expected to guide the future preparation of more capable carbon-based electrocatalysts for oxygen reduction and other electrocatalytic application.