Poly(vinyl chloride) (PVC)-based polymer electrolytes films consisting of lithium trifluromethanesulfonate (LiCF3SO3)-ethylene carbonate (EC) were prepared by the solution-casting method. Ionic conductivities of the electrolytes have been determined by an impedance studies in the temperature range of 298–373 K. Complexation of the prepared electrolytes is studied by X-ray diffraction (XRD) analysis. Thermogravimetric analysis (TGA) was used to confirm the thermal stability of the polymer electrolytes. The conductivity-temperature plots were found to followan Arrhenius nature. All these films are found to be thermally stable until 132–167°C.