AbstractRegulating 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 OC_quasi), thus leading to the electron rearrangement with a diluted spin polarization. The declined population of unpaired electrons in d_z², d_xz and d_yz 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 OC_quasi 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.