A gel polymer electrolyte (GPE) is prepared from tri(ethylene glycol) dimethacrylate monomer, benzoyl peroxide, and 1.0M LiPF6/ethylene carbonate:diethyl carbonate (1:1vol.%). The LiCoO2|graphite cells are assembled and their electrochemical properties are evaluated at various current densities and temperatures. The viscosity of the precursor containing 5vol.% tri(ethylene glycol) dimethacrylate monomer is around 4.6mPas. The ionic conductivity of the gel polymer electrolyte at 20°C is around 5.9×10−3 Scm−1. The gel polymer electrolyte has good electrochemical stability up to 4.5V versus Li/Li+. The capacity of the cell at the 1.0C rate is 89% of the discharge capacity at the 0.2C rate. The capacity of the cell at temperature of −10°C is 81% of the discharge capacity at 20°C. The discharge capacity of the cell with gel polymer electrolyte is stable with charge–discharge cycling.