A novel polymer membrane of poly(vinylidene fluoride-hexafluoropropylene) (PVdF-HFP) co-polymer was prepared by the phase inversion technique with two different non-solvents, 1-butanol or hexane. The prepared films were analyzed by scanning electron microscope (SEM) and nitrogen absorption/desorption techniques. The change in the morphology and pore diameter of the films prepared with different non-solvents correlates with the structure of the non-solvents used. This electrolyte membrane was coupled with a nanocomposite LiAl0.01Co0.99O2 cathode which was prepared by a solid-state reaction method and subsequently by ball-milling. Lithium cells consisting of LiAl0.01Co0.99O2/polymer electrolyte/Li were assembled and their charge–discharge studies were investigated.