High-efficient and durable electrocatalysts for oxygen reduction and oxygen evolution reaction (ORR/OER) are desirable to Zn-air batteries (ZABs). However, most of catalysts in powder form with sole active sites remain challenging in achieving the satisfactory bifunctional catalysis and suffer from peeling off during the long-term operation. Herein, hybrid CoFe active sites are constructed containing nanoalloys (≈10 nm), clusters (< 2 nm), and single atoms on aerophilic carbon fiber membranes as binder-free air cathodes for ultra-long-life ZABs. In particular, the high air-permeability of membranes (0.2 s) can prevent the active sites from blocking by O bubbles and promote the mass transfer. The theoretical and experimental results confirm that the hydrophilic CoFeO/CoFeOOH sites reconstructed on the surface of CoFe nanoalloys are mainly responsible for OER. While for single atoms and clusters on nitrogen (N)-doped carbon matrix, they play a synergetic role in optimizing the adsorption energy to enhance ORR activity. Thus, the as-prepared catalysts exhibit an ultra-low ORR/OER potential gap (0.64 V). When further assembled as freestanding air-electrodes, it exhibits an outstanding cycling lifespan of 1200 and 155 h in liquid- and quasi-solid-state ZABs respectively, which are fivefold and twofold higher than those of powder-based cathodes (240/67 h).