LAUSR

Regulating the electronic states of single atomic sites around the Fermi level remains a major concern for boosting the electrocatalytic oxygen reduction reaction (ORR). Herein, a Fe d‐orbital splitting manner modulation strategy by constructing axial coordination on FeN4 sites is presented. Experimental investigations and theoretical calculations reveal that the axial tractions induce the distortion of square‐planar field (FeN4 SP), up to the quasi‐octahedral coordination (FeN4O1 OCquasi), thus leading to the electron rearrangement with a diluted spin polarization. The declined population of unpaired electrons in dz2, dxz and dyz states engenders a moderate adsorption of ORR intermediates, thereby reinforcing the intrinsic reaction activity. In situ infrared spectroscopy further demonstrates that the reordering of d‐orbital splitting and occupation facilitates the desorption of *OH. The FeN4O1 OCquasi exhibits a dramatic improvement of kinetic current density and turnover frequency, which are fivefold and tenfold higher than those of FeN4 SP. This work presents a novel understanding on improving the electrocatalytic performance through the orbital‐scale manipulation.