A nonequilibrium model of the catalytic distillation was developed for the process of DMC synthesis by a urea methanolysis method over a solid base catalyst at the bench scale, and the Wilson model was used to account for the nonideality of the liquid phase. The superiority of the catalytic distillation on the removal of the products to restrain the reverse reaction was illustrated in the present work. Furthermore, the influence of total pressure and the reaction temperature on DMC yield and the sensitivity analysis to the reaction kinetics were discussed in detail. The results revealed that the catalytic distillation was appropriate for the process of DMC synthesis.