Crosslinked PVA membranes were fabricated by solution casting of the substituted PVA (SPVA), synthesized by the reaction of PVA with glycidyl acrylate (GMA) without catalyst in different molar ratios [-OH(PVA)/GMA], followed by electron beam irradiation. The chemical changes in the SPVA compared to PVA were confirmed from H-NMR and FT-IR analysis. Crosslinking degree and dimensional stability of the crosslinked PVA membranes also investigated by measuring gel fraction and dimensional change of the membranes under acidic and basic solution.