Development of high-performance oxygen reduction reaction (ORR) catalysts to replace the noble metal-based materials is critical for energy applications. Fullerenes, in the form of carbon cage with the intrinsic curvature and pentagons, have been theoretically simulated as promising ORR catalysts via atom doping and defect modification. However, fullerene-based catalysts remain challenging in achieving ORR performance comparable to Pt/C given the lack of fullerene host-dopant synergism. A rational strategy is to anchor active species on fullerene cage to enhance ORR response. Herein, a Fe, N-decorated fullerene derivative (N-methyl-2-ferrocenyl-pyrrolidinofullerene C60) is activated under NH3 stream to achieving porous Fe3O4/N-C nanomaterials with high catalytic activity toward ORR. The optimal NH3-etching temperature of 700 °C gives rise to open-pore structures, large surface area, favorable N doping, active Fe3O4 sites and short-range ordered nanographene. Through these synergetic effects, the fullerene-derived FMN700 exhibits superior ORR activity, along with respectable durability and tolerance to methanol, which surpass most of the reported fullerene-based carbon materials. This work provides a new strategy for the design and synthesis of porous carbon composites as a new class of catalysts for high-performance ORR.