Polyvinyl alcohol (PVOH) has been chemically modified by crosslink copolymerization of acrylic acid (AA) and hydroxyethylmethacrylate (HEMA) in aqueous solution of PVOH and finally crosslinking PVOH to produce a full interpenetrating network (IPN) membrane termed as PVAH. Accordingly, three such full crosslink IPNs membranes, i.e. PVAHI, PVAHII and PVAHIII containing varied weight ratio of PVOH and copolymer have been synthesized and used for pervaporative separation of methanol from its mixtures with toluene. For comparison, a conventional PVOH membrane crosslinked with glutaraldehyde has also been used for the same pervaporation study. The flux and selectivity of these IPN membranes were found to be much higher than the conventional glutaraldehyde crosslinked PVOH membrane. Among the three membranes, PVAHII with 50 wt% polyAH incorporation showed optimum performance in terms of flux and methanol selectivity. (C) 2009 Published by Elsevier B.V.