Strengthening the operational durability of oxygen reduction reaction (ORR) catalysts is essential for advancing both fuel cells and metal–air batteries. However, developing highly active and durable catalysts remains a significant challenge. In this study, a catalyst (Co/Cu–N–C) featuring uniformly distributed Co nanoparticles (NPs) and Co/Cu sites has been synthesized via a facile complex-assisted pyrolysis strategy. We observed that Cu–N–C support effectively confines the growth and leaching of Co NPs during both synthesis and ORR catalysis, thereby boosting the stability of the catalyst. Meanwhile, the presence of Co NPs and Cu sites slightly contributes to the ORR activity by optimizing the *OH desorption. The assembled zinc–air battery (ZAB) demonstrates a superhigh power density of 256.1 mW·cm⁻² and a long-term operational stability exceeding 500 h. This work not only underscores the potential of bimetallic systems and NPs in enhancing catalyst stability but also provides valuable insights for the synthesis of high-performance ORR electrocatalysts.

The bioinspired Fe-N-C features an asymmetric Fe-N₅ configuration to produce active metal-oxygen intermediates by introducing axial N ligand into a symmetric Fe-N₄ structure, enabling highly active oxygen reduction reaction (ORR). However, the artificial creation of active Fe-N₅ configuration with a direct, facile and green method has been rarely developed yet, as current techniques involve complex processes and costly precursors. Herein, we advance a novel solid-state stepwise temperature-programmable (SST) route to directly produce bioinspired Fe-N₅-C. We then demonstrate that such a Fe-N₅-C exhibits a quite higher half-wave potential (0.92 V) with 22-fold faster ORR kinetics (15.6 mA·cm⁻² @ 0.85 V) over that of the commercial Pt/C counterpart. Indeed, we perform density functional theory (DFT) to find that the Fe is discharged with an extra 0.1 e⁻ through the axially coordinate N ligand, which significantly enhances the ability to activate O₂ and enables an easier desorption of the crucial intermediate *OH on the Fe-N₅ configuration over the conventional Fe-N₄ structure.