Hybrid solid polymer electrolytes (HSPEs) of high ionic conductivity were prepared using poly acrylonitrile (PAN), poly ethylene oxide (PEO), propylene carbonate (PC), ethylene carbonate (EC) and LiCF3SO3. These electrolyte films were free standing and dimensionally stable. The HSPE films were characterised by X-ray diffraction, FTIR and a.c. impedance spectroscopic techniques. Conductivity studies of these polymer electrolytes were carried out in the temperature range 301-373 K.