This study is related to the synthesis of photopolymer bearing pendant cinnamic ester and cyclic carbonate groups by the addition reaction of poly(glycidyl methacrylate-co-acrylonitrile) [poly(GMA-co-AN)] with carbon dioxide and then with cinnamoyl chloride. Quaternary ammonium salts showed good catalytic activity for the synthesis of [poly(CNMA-co-DOMA-co-AN)]. The conversion of poly(GMA-co-AN) increased with the increase of alkyl chain length and the nucleophilicity of counter anion of the quaternary salt. Photochemical relation experiments revealed that the photopolymer had good photosensitivity even in the absence of sensitizer.