Development of efficient catalysts with low cost for the oxygen reduction reaction (ORR) plays an important role in the commercialization of fuel cells. Herein, we reported a facile method to synthesize Fe-N co-doped porous carbon (Fe-N/C) by using green media ionic liquids 1-butyl-3-methylimidazolium tetrachloridoferrate ([Bmim][FeCl4]) as precursor of C, N, and Fe, and spherical silica as a template through one-step pyrolysis. Electrochemical measurements show that Fe-N/C-800 possesses excellent ORR catalytic activity. The onset potential and half-wave potential are 0.964 and 0.821 V, respectively, which is close to those on the commercial Pt/C catalyst. Moreover, it exhibits better methanol tolerance and durability in comparison with the Pt/C catalyst. Good performance of Fe-N/C-800 in ORR is attributed to its abundant porous structure, large BET surface area, and the synergism of Fe and N dopants.