Highly hydrophilic interpenetrating polymer network (IPN) membranes were prepared from a mixture system of poly(4-vinylpyridine) (P4VP) and poly(vinyl alcohol) (PVA) by quaternizing crosslinking of P4VP with 1,4-dibromobutane (DBB) and simultaneous crosslinking of PVA with hexamethylene diisocyanate (HMDI). The membrane performance in pervaporation (PV) for the azeotropic mixture of ethanol with a less polar organic liquid (chloroform, benzene, carbon tetrachloride, and cyclohexane) was investigated. The strength of these IPN membranes was higher than that of the cellulose acetate membrane and depended on the membrane composition. All the membranes were ethanol permselective for the azeotropic feeds and equimolar mixture feeds as well. Only the swelling degree Q of the membrane, among several physicochemical factors, showed a relationship with the separation performance for the four feeds; a lower value of Q generally corresponded to a higher separation factor and smaller permeability. The membrane composition, which exhibited an optimum membrane performance, was examined in detail for some membranes. Both the separation factor for sorption and that for diffusion far exceeded unity, but the latter was greater in most cases than was the former and dominated the overall separation. (C) 2001 John Wiley & Sons, Inc.