In the present study, the synthesis of phenoxymethyl ethylene carbonate(PMEC) from carbon dioxide and phenyl glycidyl ether(PGE) was investigated using polystyrene(PS)-montmorillonite(MMT) immobilized quaternary ammonium salts as catalysts. The catalysts were prepared by grafting of styrene(ST) and vinylbenzyl chloride(VBC) copolymer onto montmorillonite interlayers, followed by the quaternization using trialkylamines. The influence of VBC concentration, the structure of trialkylamine as quaternary ammonium salts and the type of solvents on the catalytic behavior was discused.