Different concentrations of metal chlorides/polyvinyl alcohol nanocomposites have been prepared by the typical solvent cast technique. The prepared samples were investigated by different techniques such as X‐ray diffraction, differential scanning calorimetry, and scanning electron microscope. DC and AC conductivities are examined at different temperatures and frequencies. An activation process was found in the DC conductivity versus temperature relation and the activation energy was calculated. The AC conductivity obeyed the ωS power law. The behavior of S with temperature was studied. Various dielectric parameters such as dielectric constant (ε′), dielectric loss (ε″) and loss tangent (tan δ) have been determined in the temperature range 303–443 K at different frequencies. The dielectric parameters were found to decrease with increasing frequency. The study of dielectric relaxation as a function of temperature at constant frequency shows two relaxation mechanisms. The optical band gaps and band tails were estimated from the measured absorption spectra. The applied photon energy found to affect the observed optical band gaps. © 2013 Wiley Periodicals, Inc. J. Appl. Polym. Sci., 2013