Crosslinked dense poly(vinyl alcohol) (PVA) membranes with different degrees of hydrolysis were prepared and used in sorption and pervaporation of isopropanol (IPA)/water mixtures. Partial flux of water permeation was increased with the water content in the liquid mixture, but the partial flux of IPA due to the coupling effect of sorption and permeation, had a maximum value. The degree of PVA hydrolysis and the feed temperature influenced the permeation flux and water selectivity due to crystallinity and the number of polar side groups in PVA. Thus the partial flux of water and IPA was inversely proportional to the degree of PVA hydrolysis and the selectivity of PVA for water was proportional to the hydrolysis level of PVA.