Abstract: | 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. |