The active sites on oxygen electrocatalyst and the number of inherent active species are important factors affecting the performance of Zn-air battery. Constructing multiphase interfaces is an effective strategy to increase the number of active species for oxygen electrocatalysts. In this work, the number of intrinsic active species of spinel oxygen electrocatalyst was increased and its catalytic activity was enhanced by the synergistic action of bimetallic center three interfaces and heteroatom-doped carbon nanostructures. The resulting NiCo2O4/NCNTs/NiCo as catalyst exhibits superior activity toward ORR (E1/2 = 0.83 V, JL = −5.38 mA cm−2) and OER (Ej10 = 1.58 V). Further, the obtained catalyst work as a cathode assembles as Zn-air battery with a high open-circuit potential of 1.51 V and excellent cycle stability (586 h). Theoretical results indicate that the desorption of *OH species is the rate-determining step for ORR, the multiphase interfaces in the NiCo2O4/NCNTs/NiCo will provide additional electrons due to the upward shift of antibonding orbitals relative to the Fermi level. Consequently, it boosts the oxygen adsorption and charge transfer and accelerate the reaction kinetics. This work emphasizes the synergistic effect between multiphase interfaces in transition metal composite catalysts and opens up a promising way for the preparation of efficient and stable transition metal electrocatalysts. •A unique triphasic interfacial structure catalyst has been synthesized by a simple strategy.•The ultra-thin carbon layer catalyzed by NiCo alloy facilitates interfacial charge transfer.•The obtained catalyst exhibits excellent oxygen catalytic performance for zinc-air battery.