The mass production of graphene and nitrogen-doped (N-doped) graphene constitutes one of the main obstacles for the application of these materials. We demonstrate a novel resin-based methodology for large-scale self-assembly of the N-doped graphene. The N-doped graphene is readily obtained by using a precursor containing nitrogen and metal ions. The N-doped graphene is characterized by Raman, AFM, TEM, SEM, synchronic radiation and XPS measurements. The electrochemical performance of the catalyst made with such materials is investigated by a rotating ring-disk electrode (RRDE) system. The results reveal that the N-doped graphene is a selective catalyst and possesses an outstanding electrocatalytic activity, long-term stability, and good methanol and CO tolerance for oxygen reduction reaction (ORR).