The use of zinc glutarate (ZnGA) as a heterogeneous catalyst for the copolymerization of epichlorohydrin, an epoxide with an electron-withdrawing substituent, and CO2 is reported. This catalyst shows the highest selectivity (98%) for polycarbonate over the cyclic carbonate in epichlorohydrin/CO2 copolymerization under mild conditions. The (epichlorohydrin-co-CO2 ) polymer exhibits a high glass transition temperature (Tg ), 44 °C, which is the maximum Tg value obtained for the (epichlorohydrin-co-CO2 ) polymer to date.