Separation of methylphenyldiethoxysilane from synthetic fluid was carried out by batch distillation, meanwhile the process was simulated with Aspen Plus 7.0 software. The results showed that chlorobenzene and methyltriethoxysilane were pre-separated under atmospheric pressure, then methylphenyldiethoxysilane was purified under the pressure of 5 kPa and reflux ratio at 3, the resulting product had the purity of 99.67% with the single pass yield of 70.56%. The feasibility of methylphenyldiethoxysilane separation process by batch distillation was verified by experiments and simulation model with Aspen Plus 7.0 as well. The relative error between simulation and experimental result was less than 8%, which could provide basic data for industrialization.