Atomically dispersed porphyrin-type iron catalysts have demonstrated great potential to substitute platinum group metals for the oxygen reduction reaction (ORR), yet being subjected to limited active sites and sluggish O₂ activation kinetics over the symmetrical planar four-coordinated FeN₄ structure. Herein, the charge regulation on FeN₄ site is achieved via non-bonding interaction of adjacent nitrogen over high-loading single atomic Fe catalysts to boost their intrinsic ORR activity. The single atomic Fe catalysts exhibit excellent alkaline ORR activity with a half-wave potential of 0.914 V versus reversible hydrogen electrode and tenfold higher kinetic current density than that of Pt/C catalysts. Both experimental and theoretical studies confirm that the secondary nitrogen compensation can anchor greater Fe atoms up to 5.44 wt% with sufficient O₂ activation sites and simultaneously break the symmetrical charge distribution of FeN₄ site to optimize the adsorption/desorption of oxygen intermediate for accelerating ORR kinetics. Moreover, the single atomic Fe catalysts demonstrate great practical application in liquid and solid zinc-air batteries with long-term cycling stability for 600 and 150 h, respectively, as well as superior flexibility in solid batteries.