Pervaporative separation of acetone/water and isopropanol (IPA)/water systems has been studied in the water-lean range of composition of the feed mixtures. Poly(vinyl alcohol) (PVA) membranes crosslinked with citric acid, adipic acid, maleic acid, glutaraldehyde, and glyoxal were used for this purpose. The sorption characteristics of all the membranes indicate that these membranes have a good sorption selectivity for water in view of the hydrophilic nature of PVA. The type of crosslinker used for crosslinking has been shown to have an important bearing on the permeation characteristics of the membranes. Thus, the trifunctional citric acid yields the highest selectivity but lowest flux. A comparison of the productive capacities of the various membranes indicates that the glutaraldehyde crosslinked membrane has the maximum productive capacity for IPA dehydration whereas maleic acid crosslinked membrane yields the highest productive capacity for acetone dehydration.