To improve the energy conversion efficiency and durability of zinc-air batteries (ZABs) for large-scale implementations, here we propose an "air-breathing" strategy to significantly enlarge triple-interfaces with intensified mass transfer. By dip-coating the aerophilic perfluorochemical compounds (PFC) and amphiphilic ionomers into the self-supported electrodes, (1) the high solubility of O 2 in the PFC nanoemulsions greatly increases triple-phase boundaries and facilitates the efficient supply/removal of O 2 from the electrolyte; (2) the ionomers with hydrophobic and hydrophilic functionalities enable fast gas, water, and ion transport to the triple-phase boundaries; and (3) the self-supported electrode without binder ensures fast electron transfer while the firm integration prevents catalyst shedding. By applying this strategy, the ZABs show a high power density of 115 mW cm -2 and a narrow discharge/charge gap of 0.64 V at 10 mA cm -2 and a long-cycling durability (over 1000 h). This work provides a universal approach to promote gas-evolving reactions for electrochemical applications.