Activated carbon (AC) is an environmentally sustainable oxygen reduction reaction (ORR) catalyst and widely used in MFCs due to its intrinsic high specific surface area and mesoporous characteristics, but it shows relatively high ORR over-potential thus low electrocatalytic activity. In this study, a method of doped carbon modification was employed to decrease the over-potential and improve the ORR electrocatalytic activity of the AC catalyst. Nitrogen and phosphorus co-doped carbon modified AC (NPC@AC) was prepared by coating phytic acid doped polyaniline onto AC through in situ oxidative polymerization and subsequent high-temperature pyrolysis. The as-prepared NPC@AC possessed a large surface area of ∼649.3 m² g⁻¹ inherited from AC and a low ORR over-potential with a highly positive onset potential of +0.22 V vs. Ag/AgCl from NPC, thus showing an enhanced ORR electrocatalytic activity in neutral solution compared to the pristine AC, and even better than the pure NPC. The air-cathode MFC using the NPC@AC catalyst generated a much higher open circuit voltage of 0.753 V and two times higher power density of 1223 mW m⁻² than that using the pristine AC catalyst of about 0.432 V and 595 mW m⁻², respectively.