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 333 K. (C) 2004 Elsevier B.V. All rights reserved.