Developing efficient electrocatalysts for ORR/OER is the key issue for the large-scale application of rechargeable Zn-air batteries. The design of Co and N co-doped carbon matrices has become a promising strategy for the fabrication of bi-functional electrocatalysts. Herein, the surface-oxidized Co nanoparticles (NPs) encapsulated into N-doped hierarchically porous carbon materials (Co/NHPC) are designed as ORR/OER catalysts for rechargeable Zn-air batteries via dual-templating strategy and pyrolysis process containing Co2+. The fabricated electrocatalyst displays a core-shell structure with the surface-oxidized Co nanoparticles anchored on hierarchically porous carbon sheets. The carbon shells prevent Co NP cores from aggregating, ensuring excellent electrocatalytic properties for ORR with a half-wave potential of 0.82 V and a moderate OER performance. Notably, the obtained Co/NHPC as a cathode was further assembled in a zinc-air battery that delivered an open-circuit potential of 1.50 V, even superior to that of Pt/C (1.46 V vs. RHE), a low charge-discharge voltage gap, and long cycle life. All these results demonstrate that this study provides a simple, scalable, and efficient approach to fabricate cost-effective high-performance ORR/OER catalysts for rechargeable Zn-air batteries.