To simulate the centrifugal short-path distillation process, both two phases and interfacial transport are taken into account simultaneously for the first time. A new computational fluid dynamics model based on the volume-of-fluid and species transport methods is built up to analyze the detailed flow and transfer characteristics. A binary system with dibutyl phthalate-dibutyl sebacate (DBP-DBS) is used as an example for the investigation with both numerical and experimental methods. The residence time and the effects of operating parameters such as evaporator temperature and feed flow rate are explored comparatively. The simulation result for the liquid-film thickness shows a satisfactory agreement with literature data. On the basis of the simulation results, we may also obtain detailed characteristics of the heat and mass transfer such as gradients in temperature and concentration and the liquid overall mass transfer coefficient.