New poly(ethyl methacrylate) and poly(2-ethoxyethyl methacrylate) gel electrolytes containing immobilised lithium perchlorate solution in propylene carbonate were prepared by UV radical polymerisation. Materials exhibit high ionic conductivity up to 0.23mScm−1 and long-term stability of chemical and mechanical properties. Both materials keep their suitable conductivity above −20°C. The effect of material composition, temperature, cross-linking agent and salt concentration on the electrochemical and mechanical properties were studied using impedance spectroscopy and cyclic voltammetry. The accessible electrochemical window of both polymer electrolytes was estimated from −2.1 to 1.5V versus Cd/Cd2+. Impedance measurements showed almost one-order increase of conductivity when ethylene dimethacrylate was used as a cross-linking agent in comparison with the polymer electrolyte without agent.