The oxygen reduction reaction (ORR) kinetics are well known to strongly rely on the activives of electro-catalysts. Herein, a Fe-N-doped porous carbon-based electrocatalyst combined with zinc (Zn)-based metal-organic frameworks (MOFs) (Fex-N@MOF) was designed and successfully fabricated via a facile process combined immersion doping and pyrolysis. By controlling the formation of Fe3C, the physical structure of porous carbon was significantly altered, and the active chemical sites of Fe species can be formed to catalyze ORR. The uniform N-doped three-dimensional interpenetrating network structure yielded a high surface area. Both Fe3C and Fe-Nx could offer an abundance of active sites and thus promoted Fe0.05-N@MOF to exhibit high ORR activity in alkaline, neutral and acid electrolytes. Fe0.05-N@MOF showed extraordinary stability and methanol tolerance under a varied pH range conditions, it could be applied as cathode elec-trocatalyst in different fuel cells such as Zn-air fuel cell (ZFC), microbial fuel cells (MFCs), as well as direct methanol fuel cell (DMFC). Fe0.05-N@MOF is a promising material to replace Pt-based electrocatalysts as non-precious metal catalysts.(c) 2023 Elsevier B.V. All rights reserved.