We present a new design of a lithium-ion gel polymer battery which is fabricated using a semi-interpenetrating network (semi-IPN) type gel polymer and LiCoO2, covered by an ion conductive polyurethane. A 7wt.% solution of a semi-IPN gel polymer, composed of a fully cyanoethylated cellulose derivative and multifunctional poly(oxyethylene)methacrylate has an ionic conductivity of 2.7×10−3 Scm−1 at 25°C, and has a higher degree of control of liquid electrolyte evaporation when compared with conventional fluoride polymer gels. Another ion conductive polymer, a caprolactone segmented polyurethane, arranged on the surface of the cathode active material in order to increase the start temperature of the thermal runaway reaction worked as planned, raising the exothermic decomposition temperature by 50°C. A large (2500mAh) cell showed good discharge performance and improved safety characteristics as judged by a nail penetration test. Furthermore, this battery system exhibited a unique phenomenon, that of preventing overcharging. The new design of this lithium-ion gel polymer battery could be promising for large batteries that must be inherently safe, such as batteries for mobile applications.