AbstractCobalt–nitrogen–carbon is hitherto considered as one of the most satisfactory alternatives to precious metal catalysts for oxygen electrocatalysts. However, precisely tuning the local coordination of Co sites and thus engineering d‐orbital electron configuration to optimize the binding energy of the intermediates remains a huge challenge. Herein, a robust electrostatic self‐assembly strategy is developed to engineer penta‐coordinated Co sites by introducing axial O ligands with atomic‐level precision to form CoN₄O₁ configurations on MXene nanosheets (CoN₄‐O/MX). The optimized CoN₄‐O/MX demonstrates outstanding bifunctional electrocatalytic performance with a small potential gap of 0.72 V, significantly outperforming the cobalt–nitrogen–carbon catalyst with plane‐symmetric CoN₄ sites and precious metal counterparts. The Zn–air batteries integrated with CoN₄‐O/MX provide an outstanding peak power density of 182.8 mW cm⁻² and a long‐term cyclability for 250 h. Density functional theory calculations reveal that CoO coordination induces electronic delocalization to draw off partial electrons from the dz² orbital, which forms unsaturated orbital filling and lifts the energy level, resulting in a stronger Lewis basicity to facilitate electron injection into the intermediate. The study presented here provides not only a novel methodology to achieve precise control of heteroatom coordination, but also a fundamental understanding about the structure–activity relationships of d_z2 orbitals.