Development of non-precious metal-based catalysts for substituting precious catalysts as electrocatalytic oxygen reduction reaction (ORR) is crucial for energy devices, such as metal-air batteries and fuel cells. Herein, Co nanoparticles embedded in sea-urchin like N-doped carbon nanotubes (CoZn-NCNTs) composite is constructed by a facile zinc assisted epitaxial growth pyrolytic strategy of bimetallic zeolitic imidazole frameworks (ZIFs)-derived engineering. It does not require the introduction of additional carbon source and reducing ambient. During the pyrolytic process, the formation and decomposition of Co₃ZnC accompanied with the volatilization of zinc play important role for the in-situ growth of CNTs. The synergizing of N-doped CNTs and embedded Co nanoparticles structures endows excellent ORR activity of a half-wave potential of 0.82 V, together with superior stability (only 11 mV negative shift for 5000 cycles). It is much higher than the benchmark catalysts respectively derived from zinc- and cobalt-based MOF precursors. A Zn-air battery assembled with CoZn-NCNTs as ORR catalyst delivers a high-power density of 214 mW cm⁻², excellent rate capability and outstanding long-term stability with a voltage retention of 99.4%, surpassing state-of-the-art Pt/C catalyst.