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Using Chinese rice wine lees as a highly accessible and green carbon source, a new synthetic strategy has been developed for the facile and green fabrication of a N and S co-doped porous carbon (NSHPC) material via a facile carbonization and activation process. The obtained NSHPC samples possess a hierarchical porous structure with a large specific surface area and perform quite well in a supercapacitor. The prepared NSHPC electrode achieves a quite high capacitance of 433.5 F g–1 at 1 A g–1 in a 6 M KOH electrolyte, excellent rate capability, and good cycle stability. In particular, the prepared electrode can still achieve a high specific capacitance of 307.8 F g–1 when 50 mg of electroactive materials is loaded. The assembled NSHPS-based symmetric capacitor exhibits a high energy density of 17.8 Wh kg–1 at a power density of 450 W kg–1. This study provides an efficient and green strategy for preparing a high-performance N and S co-doped porous carbon material for energy storage applications.