Exploring non‐precious metal catalysts for the oxygen reduction reaction （ORR） is essential for fuel cells and metal–air batteries. Herein, we report a Fe‐N‐C catalyst possessing a high specific surface area （1501 m2/g） and uniformly dispersed iron within a carbon matrix prepared via a two‐step pyrolysis process. The Fe‐N‐C catalyst exhibits excellent ORR activity in 0.1 mol/L NaOH electrolyte （onset potential, Eo=1.08 V and half wave potential, E1/2=0.88 V vs. reversible hydrogen electrode） and 0.1 mol/L HClO4 electrolyte （Eo=0.85 V and E1/2=0.75 V vs. reversible hydrogen electrode）. The direct methanol fuel cells employing Fe‐N‐C as the cathodic catalyst displayed promising per‐formance with a maximum power density of 33 mW/cm2 in alkaline media and 47 mW/cm2 in acidic media. The detailed investigation on the composition–structure–performance relationship by X‐ray diffraction, X‐ray photoelectron spectroscopy and Mo-ssbauer spectroscopy suggests that Fe‐N4, together with graphitic‐N and pyridinic‐N are the active ORR components. The promising direct methanol fuel cell performance displayed by the Fe‐N‐C catalyst is related to the intrinsic high catalytic activity, and critically for this application, to the high methanol tolerance.
