Gel polymer electrolytes (GPE) composed of poly(ethylene-co-methyl acrylate) copolymer, LiBF4-EC/EMC/PC, and silanized fumed silica are prepared. The ionic conductivity reaches 5.8×10−4 S cm−1 in the GPE containing 22% poly(ethylene-co-methyl acrylate), 65% LiBF4-EC/EMC/PC and 13% silanized fumed silica at room temperature. GPEs are free-standing films and are used to prepare thin films for rechargeable lithium-ion polymer cells. Lithium-ion polymer cells, which consist of mesophase carbon fibre anode, poly(ethylene-co-methyl acrylate)-based GPE and LiCoO2 cathode, are assembled, and their charge–discharge cycling characteristics are investigated.