The gel polymer electrolyte was prepared by radical polymerization using tetra(ethylene glycol) diacrylate and tri(ethylene glycol) dimethacrylate to investigate affect of the number of ethylene oxide. The gel polymer electrolyte showed good electrochemical stability up to 4.5 V vs. Li/Li and high ionic conductivity at various temperatures. The lithium-ion polymer batteries with the gel polymer electrolyte, tetra(ethylene glycol) diacrylate- and tri(ethylene glycol) dimethacrylate-based, also represented good electrochemical performances such as rate capability, low-temperature performances and cycleability. However, the cell with tri(ethylene glycol) dimethacrylate, which has three ethylene oxide, showed better electrochemical performance.