Gel polymer electrolytes consisting of 25wt.% P(VdF-co-HFP), 65wt.% ethylene carbonate + propylene carbonate and 10wt.% LiN(CF3SO2)2 are prepared using by a solvent-casting technique. The electrodes are for use in lithium-ion polymer batteries. The electrochemical characteristics of the gel polymer electrolytes are evaluated by means of ac impedance and cyclic voltammetry. The charge–discharge performance of lithium polymer and lithium-ion polymer batteries is examined. A LiCoO2 |gel polymer electrolyte (GPE)|mesocarbon microbeads (MCMB) cell delivers a discharge capacity of 146.8 and 144.5mAhg−1 on the first and the 20th cycle, respectively. The specific discharge capacity is greater than 140mAhg−1 for up to 20 cycle at all the current densities examined.