The synthesis of dimethyl carbonate (DMC) from methanol and carbon dioxide using potassium hydroxide as catalyst in the presence of CH3I and the effect of ionic liquid on the reaction were investigated. The results showed that KOH is an effective catalyst; the high selectivity and raised yield of DMC formation under mild conditions were achieved. However,the addition of the ionic liquid, 1-ethyl-3-methylimidazolium bromide (emimBr), can evidently accelerate the conversion of methanol and yield of the product.