Incorporation of carbonate repeating units in a poly(ε-caprolactone) (PCL) backbone used as a host material in solid polymer electrolytes is found to not only suppress crystallinity in the polyester material, but also give higher ionic conductivity in a wide temperature range exceeding the melting point of PCL crystallites. Combined with high cation transference numbers, this electrolyte material has sufficient lithium transport properties to be used in battery cells that are operational at temperatures down to below 23 °C, thus clearly demonstrating the potential of using non-polyether electrolytes in high-performance all-solid lithium polymer batteries.