LAUSR

The fine‐tuning of *OH adsorption strength serves as a crucial strategy for optimizing the oxygen reduction reaction (ORR) performance in Fe–N–C catalysts. This study proposes a comprehensive integration of theoretical predictions and experimental validation, demonstrating the rationality and feasibility of the asymmetric multiple doping of Co and B in the second coordination sphere of FeN4 (Fe, Co/NCB) to facilitate *OH desorption. Density functional theory (DFT) calculations predict that the strategic coupling of Co and B effectively modulates the hybridization behavior between the 3dz2 orbital of the Fe active sites and the 2pz orbital of *OH intermediates. This interaction elevates the occupancy of the antibonding orbitals, thereby promoting *OH dissociation. Furthermore, the enhanced stability of Fe─N bonds in the Fe, Co/NCB suppresses the demetallization process of Fe active sites. Guided by theoretical predictions, a synergistic “metal substitution and spatial confinement encapsulation” strategy is developed to synthesize Fe, Co/NCB. As expected, Fe, Co/NCB demonstrates outstanding ORR activity in alkaline and acidic electrolytes, with the assembled zinc–air batteries delivering exceptional power density and cycling stability. This study elucidates the critical role of heteroatom doping in modulating the catalytic activity of Fe–N–C catalysts.