The dehydration of aqueous alcohol solutions through asymmetric nylon 4 membranes were investigated using pervaporation processes. The formation of asymmetric pervaporation membranes are discussed in terms of the content of the nonsolvent in the casting solution, polymer concentration, and compositions of the coagulation medium. The effects of the feed composition, feed temperature, and molar volume of the alcohols on the pervaporation performances of the asymmetric membranes are discussed. A separation factor of 4.72 and a permeation rate of 0.78 kg/m2 h for the asymmetric membrane were obtained. Compared to the conventional homogeneous nylon 4 membrane, the asymmetric membrane can effectively overcome the pervaporation performances of the nylon 4 membrane for separation of water-alcohol mixtures.