Nitrogen-doped carbon materials encapsulating 3d transition metals are promising alternatives to replace noble metal Pt catalysts for efficiently catalyzing the oxygen reduction reaction (ORR). Herein, we use cobalt substituted perfluorosulfonic acid/polytetrafluoroethylene copolymer and dicyandiamide as the pyrolysis precursor to synthesize nitrogen-doped carbon nanotube (NCNT) encapsulating cobalt nanoparticles hybrid material. The carbon layers and specific surface area of NCNT have a critical role to the ORR performance due to the exposed active sites, determined by the mass ratio of the two precursors. The optimum hybrid material exhibits high ORR activity and stability, as well as excellent performance and durability in zinc–air battery.