Alternative energy conversion systems with high efficiency, low cost and environmental benignity attract increasing attention. Herein, we astonishedly found that one new M-Nx complex, cobalt corrole [Co(tpfc)(py)2] (where, tpfc=5,10,15-tris(pentafluorophenyl) corrole and py=pyridine, denoted as Co-TPFC), adsorbed on the surface of multi-walled carbon nanotube (MWNT) (namely, Co-TPFC/MWNT) displayed an outstanding electrocatalytic property towards the reduction of oxygen (O2). The resultant electrocatalyst Co-TPFC/MWNT without pyrolysis treatment or covalent binding demonstrated a direct 4e reduction of O2 to water in acid media, while producing the 2e reduction product of H2O2 in a minimal amount. Meanwhile, our catalyst exhibited better long-term durability and higher tolerance to methanol compared to commercially used high-cost Pt/C catalyst. These results suggest that the Co-TPFC/MWNT catalyst is a technologically promising candidate for practical applications in metal-air batteries and fuel cells.