Near-neutral zinc-air batteries have attracted considerable attention owing to their high theoretical energy density, enhanced electrochemical reversibility and improved compatibility with practical operating environments. However, their performance remains severely constrained by sluggish oxygen-related reaction kinetics and the accumulation of insoluble discharge products, which pronounced electrochemical polarization, inefficient charge- discharge processes and unsatisfactory energy efficiency, thereby impeding their further development. Here we report a multifunctional mesoporous carbon catalyst incorporating monodisperse bismuth single atoms and bismuth clusters as an efficient air cathode for near-neutral zinc-air batteries. The atomically dispersed Bi species synergistically promote the deposition and decomposition of discharge products during cycling, thereby improving the reversibility of the cathodic processes. Moreover, the homogeneous distribution of Bi species across the catalyst surface guides the spatially uniform deposition of discharge products within the mesoporous channels, effectively mitigating pore blockage, reducing concentration gradients and suppressing electrochemical polarization. Benefiting from this rational structural and compositional design, the assembled batteries deliver a high discharge voltage of 1.28 V and an excellent energy efficiency of 84.82% at 0.1 mA·cm-2, achieve a long cycle life up to 400 h at current densities of 0.5 mA·cm-2. This rationally designed multifunctional mesoporous catalyst provides a promising strategy for regulating discharge-product chemistry and advancing high-efficiency near-neutral zinc-air batteries.