Polyvinyl chloride (PVC)-based composite polymer electrolyte films consisting of PVC–LiCF3SO3–SiO2 are prepared by the solution-casting method. The electrical properties of the electrolyte are investigated for ionic conductivity and its dependence on temperature. The electrolyte with the highest ionic conductivity is used to fabricate a LiCoO2/PVC–LiCF3SO3–SiO2/mesocarbon microbeads (MCMB) battery. The charge–discharge characteristics and performance of the battery at room temperature are evaluated to ascertain the effective viability, of these solid electrolytes in lithium-polymer batteries. Battery performances is also investigated at 313, 323 and 333K.