In this work, a novel hybrid composed of iron nitride and nitrogen-functionalized graphene aerogel (Fe₃N/N-GA) is fabricated and serves as the electrode material for the oxygen reduction reaction (ORR). The Fe₃N/N-GA obtained at the pyrolysis temperature of 900 °C, denoted as Fe₃N/N-GA-900, exhibits outstanding catalytic activity towards the ORR compared with other Fe₃N/N-GA hybrids, which may be due to the highest absolute contents of Fe–N and graphitic-N species for Fe₃N/N-GA-900. Remarkably, the fabricated Fe₃N/N-GA-900 hybrid is comparable to the benchmark Pt/C catalyst in terms of the onset potential and half-wave potential, while possessing a larger kinetic limiting current density, better methanol tolerance and better operational stability than the commercial Pt/C catalyst for the ORR in an alkaline medium, and therefore holds great promise as a replacement for the Pt/C catalyst in alkaline direct methanol fuel cells (DMFCs).