The demand for high-energy storage systems is constantly increasing, as is the interest to explore alternatives to commercially available batteries. The rechargeable Li-air battery represents an exciting opportunity to design batteries that may satisfy some of the requirements of our future by coupling the light Li metal with the inexhaustible source of O₂ of the surrounding air, resulting in high theoretical specific energy density. Currently, most of the researches on the Li-air battery comprise a cell fed with pure O₂ allowing that way to maintain long-term operation, owing to the high O₂ concentration free of contaminants. However, for many practical applications such as EV, air is the only viable option to supply the battery. In this context, moisture and gases other than O₂ may cause side reactions and corrosion. Herein, we report a facile strategy to fabricate an effective oxygen selective membrane with poly(vinylidene fluoride co-hexafluoropropylene) (PVDF-HFP) via non-solvent induced phase separation, casted as a 240 micron thin sheets for cell protection in ambient air condition. The use of different additives helps enhancing the barrier properties as well as the membrane specificity toward O₂. For instance, sacrificial silica nanoparticles (SiO₂ NPs) were incorporated into the precursor solution to create a controlled alveolar-like structure inside the membrane. The membrane was loaded with polydimethylsiloxane (PDMS) under vacuum. Another kind of additive considered is the cyclodextrine. Indeed, thanks to their unique structure, cyclodextrines are able to form host-guest complexes with hydrophobic molecules such as our polymer matrix. Nanosponges based on cyclodextrines were prepared and added to the polymer precursor solution before membrane casting. The as prepared membranes showed higher oxygen permeability and lower water permeability. Galvanostatic charge-discharge cycling tests of a Li-air pouch cell in a potential/time controlled mode showed an outstanding cycling life superior to 1500h with more than 150 cycles.