A variety of imidazolium-based ionic liquids (ILs) have been widely developed to effectively catalyze the cycloaddition reactions of CO2 and epoxides. To further improve the catalytic performance of those IL catalysts, we incorporated various metal chlorides (CoCl2, NiCl2, CuCl2, ZnCl2, and MnCl2) into silica-grafted 1-methyl-3-[(triethoxysilyl)propyl] imidazolium chloride to produce a series of heterogeneous catalysts. Catalytic reaction tests demonstrated that the incorporation of such metal ions can significantly enhance the catalytic reactivity of the silica-grafted ILs towards cycloaddition reactions of CO2 and epoxides that produce cyclic carbonates in solvent-free conditions. In addition, the effects on the catalytic reactivity of reaction parameters including reaction time, reaction temperature and CO2 pressure were investigated.