This paper introduced a new Double-effect distillation process with Heat Integration, called the double-effect feed-split distillation, in methychlorosilane distillation to separate multi-components of chlorosilane. Three kinds of types of double-effect distillation and the traditional single column distillation process were simulated using the software Aspen Plus. In the same feed condition, this paper compared the energy consumption and annual total cost of double-effect process with traditional single route. The results showed that, for the methylchlorosilane separation system, the double-effect feed-split distillation was an optimum distillation process and the double-effect feed-split distillation could save 40.08% of the annual total cost.