Replacing scarce and expensive platinum (Pt) with metal–nitrogen–carbon (M–N–C) catalysts for the oxygen reduction reaction in proton exchange membrane fuel cells has largely been impeded by the low oxygen reduction reaction activity of M–N–C due to low active site density and site utilization. Herein, we overcome these limits by implementing chemical vapour deposition to synthesize Fe–N–C by flowing iron chloride vapour over a Zn–N–C substrate at 750 °C, leading to high-temperature trans-metalation of Zn–N4sites into Fe–N4sites. Characterization by multiple techniques shows that all Fe–N4sites formed via this approach are gas-phase and electrochemically accessible. As a result, the Fe–N–C catalyst has an active site density of 1.92 × 1020sites per gram with 100% site utilization. This catalyst delivers an unprecedented oxygen reduction reaction activity of 33 mA cm−2at 0.90 V (iR-corrected; i, current; R, resistance) in a H2–O2proton exchange membrane fuel cell at 1.0 bar and 80 °C.