A gel polymer electrolyte (GPE) is prepared from polymethylmethacrylate interpenetrating polymer network, benzoyl peroxide, and 1.1 M LiPF6/EC-DEC (1:1 vol.%). The LiCoO2/graphite cells are prepared and their electrochemical properties were evaluated at various current densities and temperatures. The viscosity of the precursor containing 5 vol.% curable mixture is around 4.6 mPa s. The ionic conductivity of the GPE at 20°C is around 5.8×10−3 S cm−1. The GPE has good electrochemical stability up to 4.8 V vs. Li/Li+. The capacity of the cell at 1.0C rate is 82% of the discharge capacity at 0.2C rate. The capacity of the cell at −10°C is 86% of the discharge capacity at 20°C. Discharge capacity of the cell with GPE is stable with charge-discharge cycling.