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Low-cost biomass-derived carbon nanomaterials hold great promise as catalysts for the oxygen reduction reaction. Here, we have successfully prepared an N, S co-doped metal-free porous carbon catalyst through the synchronous pore-forming/doping technology. The thiourea plays dual roles as a porogen and dopant in the synthesis process. After coupling with thiourea, the successful doping of N and S elements in NSMP-I increase their defects, specific surface area, and pyridine nitrogen groups. These advantages result in a significant increase in the property of the catalyst. The ORR test result of NSMP-I shows that the four-electron transfer pathway is followed, and the onset potential and the half-wave potential are increased to 0.92 and 0.78 V vs. RHE, respectively. The result achieved may help contribute to provide a way and theoretical guidance for the sustainability and efficiency of agricultural and forestry waste resources. • The unique biomass of Shanxi Province (Sanbai melon peel) as the precursor were selected to synthesize carbon materials. • The preparation process is innovative for the formation of abundant pores in carbon materials. • The N/S atom co-doping is realized by the organic doping method, which is low-cost and environmentally friendly. • The synthesis carbon nanomaterials exhibit a significant increase in the property of the ORR catalyst. [ABSTRACT FROM AUTHOR]