The effects of baffles on the operation and mass-transfer characteristics in novel hollow fiber membrane contactor used in distillation were investigated. Hollow fiber membranes, coated with a 7 μm polydimethyl-siloxane, were operated as structural packing in the separation of ethanol-water solutions. The parallel flow mode was chosen for separation due to the stronger driving force of the concentration difference, in which liquid flows through the lumens of the fibers and vapor flows countercurrent-wise outside the fibers. Two baffles were installed on the shell side of the membrane contactors to enhance separation, which had a round shape with a semi-lunar hole. The results show that both baffled and unbaffled membrane contactors gave better, more productive separations than traditional packing in distillation, such as the excellent Sulzer Gauze BX structured packing. The baffled membrane contactors performed better than unbaffled ones, especially at high vapor velocities. The minimal HTU of membrane contactor with baffles could reach as low as 4.5 cm, and almost all the contactors could work well above the limit where flooding normally occurs in conventional cases. Theoretical analysis predicted that baffles helped membrane module to obtain a higher mass-transfer coefficient and a smaller mass-transfer resistance. Finally, theoretical mass-transfer coefficient and experimental value were compared as well as the contribution of each individual mass-transfer coefficients among liquid, gas and membrane.