Polymer electrolytes prepared by the complexation of lithium salts with poly(ethylene oxide) (PEO) and poly(vinylidene chloride-co-acrylonitrile) (PVdC-co-AN) will be of great use as separators in lithium polymer batteries. The amorphous nature of the blend electrolyte shows that the conductivity increases by the addition of lithium salts. The presence of C N and C = N in PVdC-co-AN are confirmed from the Fourier transform infrared studies. Among the various lithium salts studied, lithium trifluoro methane sulfonoimide [LiN(CF3SO2)(2)] based electrolyte exhibits the highest ionic conductivity of the order of 0.265 x 10(-5) Scm(-1) at room temperature. The sample having a maximum ionic conductivity PEO(80 wt%)/PVdC-co-AN(20 wt%)/LiN(CF3SO2)(2)(8 wt%) is supported by the lower optical band gap in UV-Visible analysis and low intensity in luminescence studies. Two and three dimensional topographic images of the above sample reveal the presence of micropores. Thermal stability of the prepared electrolytes is studied by thermo gravimetric/differential thermal analysis. Using differential scanning calorimetric analysis, the minimum glass transition temperature (30 degrees C) is observed for the sample doped with LiN(CF3SO2)(2). The cyclic voltammetric studies reveal the strong capacitive behavior of the prepared polymer electrolytes. The electrochemical stability windows for the prepared samples are observed using linear sweep voltammetry.