Two step modification of poly(vinyl alcohol) (PVA) by UV radiation and sol-gel process was used to prepare the modified PVA membranes. From the first step modification of PVA by UV radiation with 2-hydroxy ethyl methacrylate (HEMA) monomer, the poly(2-hydroxy ethyl methacrylate) (PHEMA) modified poly(vinyl alcohol), PVAHEMA, was obtained and characterized by Fourier transfer infrared spectra (FTIR) and optical polarizing microscopy for the chemical compositions and morphology. With the second step modification of sot-gel process, the organic-inorganic hybrid sol-gel material, PVAHEMA-SiO2 was prepared. Both of the modified PVA, (PVAHEMA and PVAHEMA-SiO2), were characterized by xray diffraction (XRD), differential scanning calorimetry (DSC), and thermogravimetry analysis (TGA). To prepare the alkaline solid polymer electrolyte, the various PVAHEMA and PVAHEMA-SiO2 membranes were immersed in 40 wt% KOH solution to form the KOH containing polymer electrolyte membranes And then their performances were conducted with ac impedance spectroscopy to evaluate the ionic conductivity through the membranes. At room temperature, the ionic conductivity increased from 0.044 to 0.073 S/cm for the PVAHEMA membrane; whereas the ionic conductivity was about 0.11 S/cm for the PVAHEMA-SiO2 membranes. Compared to other reports in references, our hybrid sol-gel membrane is a highly ionic conducting alkaline solid polymer electrolytes membrane. (C) 2009 Elsevier B.V. All rights reserved.