Dehydration of ethylene glycol by pervaporation was carried out using poly(N,N-dimethylaminoethyl methacrylate)/polysulfone (PDMAEMA/PSF) composite membranes prepared by solid/liquid interfacial crosslinking. The effects of feed water concentration and operating temperature on the pervaporation performance were investigated. The membrane performance compared favorably with other membranes reported in literature. At a feed water concentration of 1 mol%, a permeation flux of ∼1 mol/(m2 h) and a permeate water concentration of 99.7 mol% were achieved at 30 °C. The permeation flux was shown to increase with an increase in temperature, while the membrane selectivity was essentially the same. The increase in permeation flux with temperature was primarily due to the increased driving force for permeation, and the membrane permeability was shown to decrease as the temperature increased. The sorption uptake of the permeant in the PDMAEMA membrane was also studied, and it was revealed that the selective permeation of water through the membranes was derived from the diffusion selectivity.