Unique Fe and N co-doped multi-walled carbon nanotubes are designed to efficiently catalyze the oxygen reduction reaction (ORR). The preparation processes involve surface functionalization, subsequent wet impregnation and final thermal fixation of Fe-Nx species. The catalyst achieved outstanding alkaline ORR performance with a very positive half-wave potential (∼0.91 V). Theoretical calculations show that the carbon layer below the active Fe-Nx sites is beneficial to the ORR.