The modification of polyacrylonitrile membrane with ethanolamine was carried out, and the permeation characteristics in pervaporation were examined using the aqueous alcohol solutions. In pervaporation of a water/alcohol solution, preferential permeation of water was observed for all these membranes because of the hydrogen-bonding interaction. The selectivity of the modified polyacrylonitrile (PAN) membrane depended on operating temperature, but was independent on the thickness of the membrane. Furthermore, it was found that the membrane with more ethanolamine content had a higher affinity to water. The effect of feed concentration and the molecular size of the permeating species on the separation factor and permeation flux was also investigated.