Polymer blend electrolyte comprising of poly (vinylidene fluoride-co-Hexa fluoro propylene) ( PVdF-HFP), poly (methylmethacrylate) (PMMA) as host polymers and lithiumper chlorate (LiClO4) as the complexing saltwere prepared by solution casting technique. The polymer ratio conducive for preparing polymer electrolytes for lithiumbattery applications is optimized based on the characterization studies Viz. X-ray diffraction (XRD), Fourier transforminfrared spectroscopy (FTIR), Differential scanning calorimetry(DSC) and electro chemical impedance analysis. These studies confirmthe formation of polymer- salt complex and miscibility of polymers PVdF-HFP and PMMA. The room temperature electrical conductivity is found to be of the order of 10-5 S cm-1 and temperature dependence of ionic conductivity of polymer electrolyte films is elucidated.