A novel process was proposed for preparation of microporous poly(vinylidene fluoride-co-hexafluoropropylene) (PVDF-HFP) membranes by phase inversion techniques using water as the non-solvent. Being prepared by dissolving the polymer (PVDF-HFP) in the acetone/water solution with mechanical stirring, the homogenous casting solution was cast onto a clean glass plate. The microporous membranes were directly obtained after the evaporation of the solvent. Their porosities reached 70-90%. The test cells with the gel electrolytes prepared from as-prepared microporous membranes showed stable cycling capacities, indicating that the microporous membrane can be used for the gel electrolyte of lithium batteries. (c) 2005 Elsevier B.V. All rights reserved.