The ImX-MCM-41 (X = Cl, Br and I) catalysts were synthesized via grafting technique using MCM-41 synthesized by simple sol-gel method. These catalysts were characterized using FT-IR, N2-sorption, 13C CP/MAS NMR, XRD, TEM and SEM/EDS techniques. 13C CP/MAS NMR and FT-IR discovered the effective anchorage of imidazole and 1,2-dihaloethane on the MCM-41. SEM analysis images demonstrated that the catalysts comprise worm-like agglomerated structure which was alike to MCM-41. The catalysts were then used in cycloaddition of carbon dioxide and phenyl glycidyl ether under solvent less and co-catalyst free conditions. Among the prepared catalyst, ImBr-MCM-41 showed higher catalytic activity (96.7%) under ambient reaction conditions (100 °C, 20 bar initial CO2 pressure, 300 mg catalyst mass and 3 h). It was found that the use of ImI-MCM-41 and ImCl-MCM-41 resulted in a conversion of 77.3% and 26.4% respectively under the same reaction conditions. These results verified that the synergic effect owing to the strong nucleophilic characteristics of Br− and amine could have promoted the reaction efficiently. The catalyst was reproduced and reused four times without a substantial decrease in performance or product selectivity. A possible site for CO2 activation by ImBr-MCM-41 catalyst has been proposed.