The hybrid plasticized polymer electrolyte composed of the blend of poly(vinyl chloride) (PVC) and poly(acrylonitrile) (PAN) as host polymer, propylene carbonate 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. © 2009 Wiley Periodicals, Inc.