The development of low-cost electrocatalyst with high efficiency is crucial in energy conversion and storage. The Co/Co3O4 nanoparticles are encapsulated into N-doped porous carbon (Co/Co3O4/NPC) by one-step dual-template method. Co/Co3O4/NPC possesses hierarchically porous structure consisting of 3D ordered macroporous carbon frameworks and mesopores with large BET surface areas, and Co/Co3O4 nanoparticles are uniformly enclosed in the carbon walls. Co/Co3O4/NPC exhibits better durability in alkaline solution for oxygen reduction reaction (ORR) and oxygen evolution reaction (OER) compared to commercial PVC and Ir/C. Such superior catalytic performance could be ascribed to the synergistic effects between embedded Co/Co3O4 nanoparticles and the unique hierarchically porous structure.