Phosphorus (P)/sulfur (S) co-doped porous carbon derived from resorcinol and furaldehyde are synthesized through one-step sol-gel processing with the addition of phosphorus pentasulfide as P and S source followed with freeze-drying and pyrolysis in nitrogen. The P/S co-doping strategy facilitates the pore size widening both in micropore and mesopore regions, together with the positive effect on the degree of graphitization of porous carbon through elimination of amorphous carbon through the formation and evaporation of carbon disulfide. As an electrode for supercapacitor application, P/S co-doped porous carbon demonstrates 43.5% improvement on specific capacitance of the single electrode compared to pristine porous carbon in organic electrolyte at a current of 0.5 mA due to the P-induced pseudocapacitive reactions. As for electrocatalytic use, promoted electrocatalytic activity and high resistance to crossover effects of oxygen reduction reaction (ORR) in alkaline media are observed after the introduction of P and S into porous carbon. After air activation, the specific capacitance of the single electrode of sample PS-pC reaches up to 103.5 F g−1 and an improved oxygen reduction current density.