Organic-inorganic hybrid membrane in which nanoscale hybrid domains creating preferential pathways for selective permeation exhibits excellent performance in separation processes. Herein, a synthesis route of sol-gel reaction in acidified and hydrated ethanol to prepare silica-poly (vinyl alcohol) hybrid membrane of nanoscale homogeneity is reported. 29 Si NMR study was performed on the membrane samples to probe the connectivity of SiO4 tetrahedra in the cross-linking hybrid networks while the small-angle scattering study revealed nanostructure of the silica-polymer hybrid. TEM, DSC, IR, TGA, XRD and swelling studies were performed to study other physico-chemical properties of the membrane. The hybrid membrane exhibited superior water permeability 96 L m -2 h -1 µm than the other reported membranes in pervaporation desalination of saline water of 2000 ppm NaCl.