Novel polymer blend electrolyte was prepared using poly (ethylene oxide), poly(vinyl chloride) and lithium perchlorate (LiCIO) as the complexing salt by employing solvent casting technique. The prepared films were subjected to XRD, FFIR, a.c impedance spectroscopy and thermogravimetry / differential thermal analysis (TG/DTA). Quantitative analysis of the FTIR spectra provides the specific interactions between the constituents. The thermal stability of the film is found using TG/ DTA studies. The maximum conductivity value of PVC (25)-PEO(75)- LiClO4(8) film is found as 1.32 × 10-5 S/cm at room temperature. As the PVC concentration increases in the electrolyte, the conductivity is found to decrease. The temperature dependent ionic conductivity is also carded out in the temperature range 303-333K and the results are discussed. © 2007 IACS.