Bifunctional electrocatalysts with high catalytic property for the oxygen reduction reaction (ORR) and oxygen evolution reaction (OER) are vital for high-performance zinc–air batteries (ZnABs). In this study, an efficient bifunctional electrocatalyst with hollow structure (C–N/Co (1/2)) has been successfully prepared through carbonization of ZIF-8@ZIF-67 and evaporation of Zn ions at high temperature. With Co nanoparticles encapsulated by an N-doped porous carbon matrix, the catalyst exhibits excellent stability in aqueous alkaline solution over an extended period and good tolerance to the methanol crossover effect. The integration of an N-doped graphitic carbon outer shell and Co nanoparticles enables high ORR and OER activity, as evidenced by ZnAB using the catalyst C–N/Co (1/2) in an air cathode.