Fe-N-C materials with atomically dispersed Fe–N₄ sites could tolerate the poisoning of phosphate, and is regarded as the most promising alternative to costly Pt-based catalysts for the oxygen reduction in high temperature polymer electrolyte membrane fuel cells (HT-PEMFCs). However, they still face the critical issue of insufficient activity in phosphoric acid. Herein, we demonstrate a P-doping strategy to increase the activity of Fe-N-C catalyst via a feasible one-pot method. X-ray absorption spectroscopy and electron microscopy with atomic resolution indicated that the P atom is bonded with the N in Fe–N₄ site through C atoms. The as prepared Fe-NCP catalyst shows a half-wave potential of 0.75 V (vs. reversible hydrogen electrode (RHE), 0.1 M H₃PO₄), which is 60 and 40 mV higher than that of Fe-NC and commercial Pt/C catalysts, respectively. More importantly, the Fe-NCP catalyst could deliver a peak power density of 357 mW·cm⁻² in a high temperature fuel cell (160 °C), exceeding the non-noble-metal catalysts ever reported. The enhancement of activity is attributed to the increasing charge density and poisoning tolerance of Fe–N₄ caused by neighboring P. This work not only promotes the practical application of Fe-N-C materials in HT-PEMFCs, but also provides a feasible P-doping method for regulating the structure of single atom site.