Transition metal–carbon–nitrogen catalysts for the oxygen reduction reaction (ORR) are promising and challenging. Cu is a potential transition metal to form efficient ORR catalysts for fuel cells. Herein, a facile method is developed to synthesize a highly dispersed Cu−N_X and N-doped graphene (Cu−N−G) catalyst. The Cu−N−G catalyst shows a half-wave potential (E_1/2) of 0.859 V, which is comparable to the commercial Pt/C catalyst (0.856 V), and is among the best compared with the previously reported Cu-based materials. In addition, such a catalyst shows good stability and methanol tolerance in alkaline media. A synergy of doped N (pyridinic and graphitic N) and Cu−N_X moieties as well as the pore structure are revealed to account for the enhanced ORR activity.