N-doped graphene/Co nanocomposites (NG/Co NPs) have been prepared by a simple one-step pyrolysis of Co(NO3)2∙6H2O, glucose and dicyandiamide (DCDA). The products with nitrogen doped and suitable graphitic degree perform high electrocatalytic activity (with the reduction peak at −0.099V vs Ag/AgCl) and near four-electron selectivity for the oxygen reduction reaction (ORR), with excellent stability and durability in alkaline medium comparable to a commercial Pt/C catalyst. Owing to the superb ORR performance, low cost and facile preparation, the catalysts of NG/Co NPs have great potential applications in fuel cells, metal-air batteries and ORR-related electrochemical industries.