Methoxy-ethylene glycol methacrylates, CH2=CMeCOO(CH2CH2O)nMe (n = 1, 2, 3), ethoxy-triethylene glycol methacrylate, CH2=CMeCOO(CH2CH2O)3Et, and N,N-dimethylaminoethyl methacrylate, CH2=CMeCOOCH2CH2NMe2, were used to synthesise the corresponding polymers. Conductivities of these polymers complexed with lithium perchlorate were investigated. Tetraethylene glycol dimethyl ether was used as plasticiser to increase the conductivity of the materials. A conductivity of 10−5 S cm−1 was obtained at room temperature for the plasticised polymer samples. Effects of polymer structure, plasticiser, salt concentration and temperature on conductivity and glass transition temperature of the polymer electrolytes are discussed.