The hybrid plasticized polymer electrolyte composed of the blend of poly(vinyl chloride) (PVC) and poly(acrylonitrile) (PAN) as host polymer, propylene carbo ate as plasticizer, and LiClO4 as a salt was studied. An attempt was made to optimize the polymer blend ratio. XRD, Fourier transform infrared, and DSC studies confirm the formation of polymer-salt complex and miscibility of the PVC and PAN. The electrical conductivity and temperature dependence of ionic conductivity of polymer films are also Studied and reported here. (C) 2009 Wiley Periodicals, Inc. J Appl Polym Sci 113: 1651-1656, 2009