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Oxygen reduction reaction (ORR) plays a key role in the application of fuel cells. Here, we used shaddock peel to fabricate a set of N, P dual-doped hierarchical porous carbons, abbreviated as NPSPs, where the carbons were carbonized, activated and dual-doped via a simple one-step pyrolyzation. Contrast results indicate the contents of pyridinic-N, graphitic-N and P–C species increase with the rising of temperatures, and the temperature also affects the degree of graphitization, surface area, morphology, thus influences the ORR performance. More importantly, the NPSP-900 demonstrates an outstanding ORR activity with a comparable half-wave potential (0.83 V vs. RHE) and higher current density with respect to commercial Pt/C, following 4e transfer pathway. Our work illustrates that NPSP-900 is a promising cathode for fuel cells because of its simple preparation, waste utilization, excellent ORR performance, good methanol tolerance and superior stability. Image 1 • One-step pyrolysis can accomplish carbonization, activation and N,P-dual doping. • NPSPs own hierarchical porous structures with high BET surface areas. • Higher temperature can enhance ORR activities with improved doping N/P species. • NPSP-900 owns a close ORR activity compared with Pt/C, following 4e transfer way. • NPSP-900 shows a remarkable methanol tolerance and superior stability. [ABSTRACT FROM AUTHOR]