Polyvinyl alcohol (PVOH) has been chemically modified by polymerizing hydroxyethylmethacrylate (HEMA) in aqueous solution of PVOH and finally crosslinking PVOH with glutaraldehyde to produce a semi-interpenetrating network (SIPN) membrane. Accordingly, three such SIPNs i.e., SIPNI, SIPNII, and SIPNIII were synthesized with different weight ratio of PVOH: HEMA i.e., 1:0.25 (SIPNI), 1:0.50 (SIPNII) and 1:0.75 (SIPNIII). These SIPN membranes were used for pervaporative dehydration of dioxane. PVOH without any chemical modification but crosslinked with the same amount of glutaraldehyde has also been used for this study for comparison. All the SIPN membranes were also characterized with various conventional methods like mechanical properties, DSC and TGA. Water permeability and water selectivity of the IPN membranes were found to be much higher than those of the crosslinked PVOH membrane which was not chemically modified. The permeability of the membranes were also found to increase with increase in the HEMA content in PVOH matrix.