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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 Pt/C 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.