Herein, we highlight redox‐inert Zn2+ in spinel‐type oxide (ZnXNi1−XCo2O4) to synergistically optimize physical pore structure and increase the formation of active species on the catalyst surface. The presence of Zn2+ segregation has been identified experimentally and theoretically under oxygen‐evolving condition, the newly formed VZn−O−Co allows more suitable binding interaction between the active center Co and the oxygenated species, resulting in superior ORR performance. Moreover, a liquid flow Zn–air battery is constituted employing the structurally optimized Zn0.4Ni0.6Co2O4 nanoparticles supported on N‐doped carbon nanotube (ZNCO/NCNTs) as an efficient air cathode, which presents remarkable power density (109.1 mW cm−2), high open circuit potential (1.48 V vs. Zn), excellent durability, and high‐rate performance. This finding could elucidate the experimentally observed enhancement in the ORR activity of ZnXNi1−XCo2O4 oxides after the OER test. The outstanding electrocatalytic performance of Zn0.4Ni0.6Co2O4/NCNTs towards ORR/OER is validated, presenting remarkable rate capability and durability in liquid‐flow Zn–air batteries. A dual‐reinforcement mechanism in the Zn–Ni–Co ternary spinel is also proposed. Zn0.4Ni0.6Co2O4/NCNTs exhibits extreme durability and electrochemically enhanced properties, enabling its application in practical rechargeable zinc–air batteries.