Polyvinyl chloride)/Poly(ethyl methacrylate) (PVC)/(PEMA)-based blend polymer electrolytes comprising a combination of PC (Propylene carbonate) as a plasticizer and LiClO4 as a salt have been prepared by solvent casting technique with varying salt concentration ratios systematically. The prepared electrolytes were subjected to X-ray diffraction, Fourier transform infrared spectroscopy, conductivity studies, thermogravimetric/differential thermal analysis and Scanning electron microscopic studies. PVC/PEMA polymer blend electrolyte with 8 wt % of lithium, salt exhibited ionic conductivity of the order of 10-3 S/cm at room, temperature. © 2008 Wiley Periodicals, Inc.