It has long been found that the flow pattern of the liquid phase on distillation tray is of great importance on distillation process performance. But until now, there was very few published work on quantitative investigation of this subject. By combining the computational fluid dynamics (CFD) with the mass transfer equation, a theoretical model is proposed for predicting the details of velocity and concentration distributions as well as the tray efficiency of distillation tray column. Using the proposed model, four different cases corresponding to different assumptions of liquid and vapor flowing condition for a distillation tray column were investigated. In Case I, the distributions of velocity and concentration of the incoming liquid from the downcomer and the uprising vapor from the underneath tray spacing are uniform. In Case II, the distribution of the incoming liquid is non-uniform but the uprising vapor is uniform. In Case III, the distribution of the incoming liquid is uniform but the uprising vapor is non-uniform. In Case IV, the distributions of both the incoming liquid and the uprising vapor are non-uniform. The details of velocity and concentration distributions on a multiple sieve tray distillation column in four different cases were simulated using the proposed model. It is found that the shape of the simulated concentration profiles of vapor and the liquid is quite different from case to case. The computed results also show that the tray efficiency is highly reduced by the maldistribution of velocity and concentration of the incoming liquid and uprising vapor. The tray efficiency for Case I is higher than Case II or Case III, and that for Case IV is the lowest. It also reveals that the accumulated effect of maldistribution becomes more pronounced when the number of column trays increased. The present study demonstrates that the use of computational method to predict the mass transfer efficiency for the tray column, especially for the large one, is feasible.