The impending environmental problems and energy crisis have driven the rapid development of efficient and environmentally friendly metal-air battery, which is highly hampered by the inherently sluggish kinetics of oxygen evolution reaction (OER) and oxygen reduction reaction (ORR) for the air-cathode. Hence, we employed a facile electrospinning method to prepare an efficient OER/ORR bifunctional catalyst, where NiCo-based oxides nanoparticles are encapsulated in the carbon nanofibers. The thiourea is used as the dispersant to increase the nanoparticles dispersion and the acetamide is used as the oxidant to prepare the NiCo-bimetallic oxide on carbon nanofibers under protective atmosphere (N-2). The defect-rich interfaces introduced by phase interpenetration between NiCo-oxide and carbon generate abundant atomic traps that capture reactants toward catalytic sites. Furthermore, its unique one-dimensional nanofibers morphology with hierarchically macro/mesoporous nanostructure provides abundant pathways for the transportation of mass and electrons. Benefitting from above advantages, the as-prepared Zn-air battery exhibits a low charge-discharge gap, high power density (155.48 mW cm(-2)), and excellent cycling stability (lifetime over 1500 h @ 5 mA cm(-2)).