Hybrid, solid polymer electrolyte films consisting of poly(vinyl chloride) (PVC), poly(vinylidine fluoride) (PVdF), LiN(CF3SO2)(2) and ethylene carbonate (EC) are prepared using solvent casting technique. The formation of polymer-salt complex has been confirmed by FTIR spectral studies. The effect of the PVC/PVdF blend ratio on ionic conductivity is explained in terms of the morphology of the film. The highest ionic conductivity value (5.766 x 10(-3) S cm(-1)) is obtained for PVC-PVdF-LiN(CF3SO2)(2)-EC (Film F3) at room temperature. The electrochemical stability window of Film F3 was about 4.5 V determined from the linear sweep voltammetry plot. The surface morphology of the above membrane was also observed by scanning electron microscope (SEM). Polymer electrolyte film bereft of PVC appears very promising for Li battery applications. (c) 2005 Elsevier B.V. All rights reserved.