Nylon 4, which possesses high mechanical strength and good affinity for water, can be considered as a liquid separation membrane. To improve the hydrophilicity of a Nylon 4 membrane for pervaporation and evapomeation processes, and to overcome the hydrolysis of polyvinyl alcohol (PVA), this study attempts to prepare a PVA-g-Nylon 4 membrane by y-ray irradiation grafting of vinyl acetate (VAc) onto Nylon 4 membrane, followed by hydrolysis treatment. The effects of downstream pressure, irradiation dose, VAc monomer concentration, degree of grafting, feed composition, and size of alcohols on the separation of water-alcohol mixtures were studied. The surface properties of the prepared membrane were characterized by FTIR, ESCA, and a contact angle meter. A separation factor of 13.8 and a permeation rate of 0.352 kg/m'.h can be obtained for a PVA-g-Nylon 4 membrane with a degree of grafting of 21.2% for a 90-wt% ethanol feed concentration. Compared to the pervaporation process, the evapomeation process has a significantly increased separation factor with a decreased permeation rate for the same PVA-g-Nylon 4 membrane.