Sodium-ion conducting polymer electrolytes based on poly(vinyl alcohol) complexed with sodium bromide were prepared with a solution-casting technique. The structure of these films was determined with X-ray diffraction, and the complexation of the salt with the polymer was confirmed with Fourier transform infrared spectroscopy studies. Electrical conductivity was measured with an alternating-current impedance analyzer in the frequency range of 100 Hz to 1 MHz and in the temperature range of 303-373 K. It was observed that the magnitude of conductivity increased with the increase in the salt concentration as well as the temperature. The nature of the charge transport in these polymer electrolyte films was determined with both Wagner's polarization technique and the Watanabe technique. The dominant conducting species were found to be ions, particularly anions. Optical absorption studies were performed in the wavelength range of 200-600 nm, and the absorption edge, direct band gap, and indirect band gap values were evaluated. Electrochemical cells were fabricated, and their discharge characteristics were studied. (C) 2008 Wiley Periodicals, Inc.