We demonstrate a highly efficient Fe/N/C electrocatalyst for oxygen reduction reaction (ORR) which was prepared through MgO template directed approach followed by pyrolysis of iron salt and nitrogen-rich carbon precursors. The Fe/N/C electrocatalyst displays a porous carbon structure with iron atoms, Fe3C nanoparticles and Fe-N-x as active sites which endow the electrocatalyst with plenty of accessible and active sites that are favorable for the enhanced electrocatalytic activity towards ORR. The as-obtained Fe/N/C electrocatalyst exhibits excellent electrocatalytic performance for ORR matching those of the state-of-the-art commercial Pt/C with a higher catalytic activity via a four-electron transfer process, a comparable onset and half-wave potentials, and a peroxide yield lower than 10% in alkaline media. Besides, the Fe/N/C electrocatalyst displays a higher durability and negligible methanol-crossover effect compared with Pt/C electrocatalyst.