Single-atom catalysts have been extensively researched in electrocatalytic oxygen reduction and evolution reactions (ORR/OER) due to their tunable coordination environment. However, the linear scaling relationship (LSR) of oxygen intermediate adsorption energies imposes limitations in simultaneously enhancing ORR/OER. Herein, a unique asymmetrically coordinated FeN3P1 single-atom configuration coupled by Fe2P nanoparticle is synthesized via a prefabricated Fe-N/P coordination strategy. The accentuated structural distortion induced by Fe2P can effectively break the LSR, lowering the energy barriers for ORR/OER. Kinetically, a modulation of OH− concentration by Fe2P on the catalytic interface was identified by finite element simulation and molecular dynamics simulation, which can positively facilitate ORR/OER kinetics. The obtained Fe2P@FeN3P1-NC catalyst exhibits excellent bifunctional ORR/OER (∆E = 0.65 V) and a promising application in zinc-air battery. This work provides a valuable insight into simultaneous regulation of thermodynamic and kinetic behavior by tailored structure distortion and enriched surface ions for ORR/OER.