In this manuscript, we develop a novel method based on the combination of space-confined pyrolysis and second heat-treatment for the synthesis of Fe/N-doped Carbon (Fe/N/C) ORR catalyst, targeting solving the low yield, insufficient nitrogen-doped level, and nanostructure collapse problems. The silica confined space is constructed by covering an outer inorganic silica layer onto the surface Fe/Phenanthroline/C (Fe/Phen/C) precursor. Within this silica-confined space, the precursor loss, particle coagulation and structure collapse that are commonly encountered during high-temperature pyrolysis in an open system can be eliminated. Moreover, the porosity and nitrogen-doped configuration can further be tuned by a second heat-treatment process. The resultant Fe/N/C catalyst show excellent ORR activity in alkaline media, better durability and stronger methanol tolerance compared to those of state-of-the-art Pt/C catalyst. (C) 2017 Published by Elsevier Ltd.