Poly (vinyl alcohol) (PVA) membranes crosslinked with poly (styrene-co-maleic anhydride) (PSMAn) have been prepared by the solution method. To, investigate the separation behavior of the crosslinked PVA/PSMAn membranes in the pervaporation process, the selective sorption experiment and swelling measurements of the membranes in ethanol-water mixtures of 30∼90 wt% ethanol contents were conducted with equipment that was able to measure the concentration and amount of the liquid absorbed in the membranes. The membranes prepared in this study exhibited good selectivity toward water component in sorption and permeation. Also, in the feed contained ethanol more than 50 wt%, the permeation selectivity of the membrane showed better correlation with the sorption selectivity than that with the swelling ratio changing toward the crosslinking content. This behavior was consistence with a solution-diffusion model correlating permeation and sorption selectivity, and led to the conclusion that the permeation selectivity was determined by sorption rather than by diffusion step in the membrane.