A novel energy saving procedure for the synthesis and separation of dimethyl carbonate by reactive distillation is proposed, and its principle technical feasibility is demonstrated based on the physical properties of a dimethyl carbonate synthesis system. The steady-state simulation is performed with Aspen Plus, and the UNIQUAC-RK model is used in this work The simulation result shows that the novel procedure can simplify the process and reduce energy consumption. The new procedure can save energy costs by 29.50% compared with the traditional processes. For further energy consumption reduction, heat integrations between the low-pressure column and the high-pressure column are adopted. It is found that energy savings of 53.80% are achieved for this novel process. The total annual costs of the four procedures are estimated and compared. It is shown that costs can be reduced by more than 31.54% by using the new processes. To sum up, the new procedure has a better economic investment than the original.