The polymer electrolyte films based on poly(vinyl alcohol) (PVA), (NaI+4AgI) and water have been synthesized. The polymer electrolyte exhibited an ionic conductivity of ∼10-1Scm-1 and shows to be stable and constant in a wide temperature range (10–70 °C) for the hydrated samples. The Impedance spectroscopy studies were obtained from 106 to 109Hz and over the temperature range 10 to 70 °C. The results reveal three dielectric relaxations that appear in both the imaginary and real part of the permittivity. These relaxations are related with the cooperative segmental movements of the macromolecular chains, normal-mode relaxation and localized motions of the structural units.