We herein report the preparation of an Fe–N-doped carbon nanoparticle–carbon nanofiber (Fe–N-CNP–CNF) composite using a solution plasma process followed by heat treatment. The resulting Fe–N-CNP–CNF exhibits excellent catalytic activity, durability, and methanol tolerance for the oxygen reduction reaction (ORR) in an alkaline solution. The enhanced ORR activity of Fe–N-CNP–CNF can reasonably be attributed to the synergistic contributions provided by a high degree of graphitization of CNF, meso/macroporosity of CNP, presence of catalytically active sites for ORR (i.e., graphitic N and Fe–N bond), and existence of carbon-encapsulated Fe/Fe₃C particles.