Solid polymer electrolytes comprising poly(vinyl acetate) (PVAc), and poly(vinylidene fluoride-co-hexafluoropropylene) (PVdF-co-HFP), low molecular weight plasticizer [Ethylene Carbonate (EC)] and different lithium salts (LiBF4, LiClO4, and LiCF3SO3) are prepared by solution casting technique. The electrolyte films are subjected to various characterization techniques such as XRD, FTIR, DSC, SEM and ac impedance analysis. Ionic conductivity is obtained as a function of frequency at various temperatures ranging from 302 to 363 K. The maxi-mum room temperature ionic conductivity is found to be 1.18 x 10(-3) S cm(-1) for the film containing LiBF4 and the temperature dependent ionic conductivity values seem to obey VTF relation. Microstructure of the samples has been depicted by means of scanning electron microscope. (C) 2010 Wiley Periodicals, Inc. J Appl Polym Sci 118: 646-651, 2010