Polyvinyl alcohol(PVOH) has been chemically modified by crosslinking copolymerization of acrylic acid(AA) and hydroxyethylmethacrylate (HEMA) in aqueous solution of PVOH and finally crosslinking PVOH with glutaraldehyde to produce a full interpenetrating network(IPN) membrane. Accordingly, three such full crosslink IPNs i.e., PVAHI, PVAHII and PVAHIII have been synthesized with different weight ratio of PVOH: Poly (AA-co-HEMA) i.e., 1:0.25 (PVAHI), 1:0.50 (PVAHII) and 1:0.75 (PVAHIII). These IPN membranes have been used for pervaporative separation of MTBE-methanol mixtures. All the PVAH membranes were also characterized with various conventional methods like FTIR, mechanical properties, DSC and TGA. Permeability and methanol selectivity of these membranes were found to increase with increasing amount of copolymer in PVOH matrix. However, among the three membranes, PVAHIII were found to show the highest flux but lower selectivity for methanol while PVAHII membrane showed optimum performance in terms of both flux and selectivity.