This paper gives a comprehensive study on dimethyl carbonate synthesis by transesterification reaction of methanol with ethylene carbonate (EC) resulted from CO2 and ethylene epoxide, co-producing useful ethylene glycol (EG). The reaction is reversible with an EC equilibrium conversion of about 80%. The reactive distillation column is an ideal reactor to realize a completion conversion of EC. A novel experimental reactor is proposed with several flasks interlinked, and the satisfactory results are obtained. A rigorous mathematical model is developed including mass balance equation, heat balance equation, phase equilibrium equation. summation equation and reaction kinetics equation. The calculated results show a good agreement with the experimental ones. (C) 2003 Elsevier B.V. All rights reserved.