Homogeneous membranes were prepared by blending polyvinyl alcohol (PVA) with polyacrylic acid (PAA) and furthermore the blend membrane is cross-linked covalently through an ester linkage formation between a hydroxyl group of PVA and carboxyl group of PAA. These membranes were evaluated for separation of azeotropic isopropyl alcohol (IPA)/water mixtures by pervaporation, that is, a vacuum applying membrane process. The overall and preferential sorption of IPA/water mixtures in cross-linked membranes were determined to investigate the influence of PVA/PAA ratio and of liquid mixture composition. Pervaporation characteristics were also determined as a function of PVA/PAA ratio and of the feed mixture composition. With increasing PAA content in the membranes, solubilities and fluxes decreased and selectivities increased. Because of polarity, water permeated preferentially through the membranes. Sorption results showed the same tendency as pervaporation results. (C) 2003 Elsevier Science Ltd. All rights reserved.