The work aims to study the preparation and corrosion performance of ZnO anti-corrosion film, and apply it to Al-air batteries to explore the influence of the thickness and porosity on specific capacity and discharge performance. The ZnO films were prepared by electrospinning. The mixed solution of Zn(NO3)2.6H2O and PAN was used as the precursor solution and spun on the anode substrate. After heat treatment, the PAN in the fiber was decomposed and the Zn(NO3)2.6H2O was transformed. Finally, the ZnO film was obtained. The surface morphology and chemical composition were characterized by XRD, SEM and XPS. The electrochemical corrosion behavior and discharge performance were analyzed by electrochemical workstation and battery test system. The results show that the ZnO anti-corrosive film can effectively inhibit the surface self-corrosion of Al anode. The corrosion inhibition rate is affected by the thickness and porosity of the films. The corrosion inhibition rate increases with the increase of film thickness and the decrease of porosity. The corrosion inhibition rate of 8 μm ZnO anti-corrosive films can reach up to 87.55%. Compared with the Al-air battery with pure Al anode, the specific capacity of the battery with ZnO anti-corrosion film can be increased by more than 3 times. For small power density discharge, thicker anti-corrosive films can improve the specific capacity of the battery without affecting the discharge performance. For higher power density discharge, the thickness of the film must be controlled to achieve a better discharge performance. Therefore, the ZnO anti-corrosive film which can inhibit the hydrogen evolution of Al anode is prepared by electrospinning. It can be used in Al-air batteries to extend the discharge time and improve the specific capacity of the batteries. This technology could also be applied to the corrosion protection of metals in alkaline solutions.