The phosphorus (P) and iron (Fe) co-doped carbon (P-Fe-C) has been facilely synthesized via an in situ sal-gel polymerization method followed by a pyrolysis process using resorcinol and formaldehyde as the carbon source, tetraphenylphosphonium bromide as the P source and iron nitrate as the Fe source. Benefiting from the high doping content of P and Fe and large specific surface area, the as-prepared P-Fe-C electrocatalysts demonstrate considerable catalytic activity for the oxygen reduction reaction (ORR) as evidenced by rotating ring-disk electrode studies and show long-term stability superior to the commercial Pt/C (20 wt.%). The catalytic site of P-Fe-C for the ORR is proposed as Fe-P-x (x is the coordination number of P atoms to Fe) embedded in carbon. The pyrolysis temperature is found to play an important role in the microstructure, texture and the doping content of P and Fe in carbon, which further affects the catalytic activity of P-Fe-C for ORR. (C) 2014 Elsevier B.V. All rights reserved.