A novel highly porous poly(vinylidene fluoride-hexafluoropropylene) (PVdF-HFP) membrane was prepared by phase inversion method with 1-butanol or methanol as non-solvent. These films where characterized by ionic conductivity, SEM and nitrogen adsorption/desorption analysis. The prepared membranes were employed as separator in LiA1(0.01) Co0.99O2/Li cells and their charge-discharge performances are presented. Although, these membranes vary slightly in the physical properties like, morphology and surface area no discernible changes could be seen in charge-discharge studies. (C) 2004 Elsevier B.V. All rights reserved.