In summary, Li, Chen, Yang and co-workers successfully constructed atomically dispersed Sb active sites on the hierarchical mesoporous carbon framework via a molten chloride salt-assisted pyrolysis strategy, forming a unique SbN₄–Cl coordination structure. This innovative design effectively regulated the electronic structure of the Sb center through the introduction of an axial chlorine ligand, optimizing the p-band distribution and significantly reducing the adsorption energy of key intermediates such as HO^*, thereby enhancing the kinetic rate and overall catalytic efficiency of the ORR. This study not only overcomes the inherent limitation of low catalytic activity commonly observed in main-group metal catalysts but also greatly expands their application prospects in energy conversion systems such as fuel cells and metal–air batteries. Moreover, it provides new theoretical guidance and design strategies for tuning the p-band structure of main-group metal SACs through precise coordination engineering. However, the air electrode in zinc-air batteries is simultaneously governed by the oxygen evolution reaction (OER) and ORR during charge-discharge cycling. Therefore, the development of main-group metal catalysts with bifunctional ORR and OER activity in both acidic and alkaline environments is essential. In addition, from a practical perspective, substantial improvements in the long-term cycling stability and overall durability of electrode materials in zinc-air batteries are imperative.