Developing electrocatalysts with both high selectivity and efficiency for the oxygen reduction reaction (ORR) is critical for several applications including fuel cells and metal-air batteries. In this work we developed high performance electrocatalysts based on unique winged carbon nanotubes. We found that the outer-walls of a special type of carbon nanotubes/nanofibers, when selectively oxidized, unzipped and exfoliated, form graphene wings strongly attached to the inner tubes. After doping with nitrogen, the winged nanotubes exhibited outstanding activity toward catalyzing the ORR through the four-electron pathway with excellent stability and methanol/carbon monoxide tolerance. While the doped graphene wings with high active site density bring remarkable catalytic activity, the inner tubes remain intact and conductive to facilitate electron transport during electrocatalysis.