Poly(vinyl chloride)/poly(ethyl methacrylate)-based polymer blend electrolytes comprising propylene carbonate as a plasticizer and a lithium salt LiX (X = BF4-, ClO4-, CF3SO3-) are prepared by a solvent casting technique. The electrolytes are subjected to characterization by ionic conductivity, X-ray diffraction, Fourier transform infrared spectroscopy and thermogravimetic/differential thermal analysis. The electrolytes that contain LiBF4 exhibit maximum conductivity and are thermally stable up to 254 °C. © 2008 Elsevier B.V. All rights reserved.