A novel PVA/CuI nanocomposite polymer electrolyte layer synthesized via the reduction of CuCl2 by NaI in an aqueous PVA solution. The as-prepared films were characterized by X-ray diffraction, scanning electron microscope, as well as impedance spectroscopy. The obtained results indicated the formation of hexagonal CuI nano particles of ≈55 nm sizes embedded in the PVA matrix. In addition, the study of dielectric parameters and conductivity of PVA/CuI nanocomposite in wide range of temperature and frequency are given and discussed. The frequency dependence of ac-conductivity suggests power law with an exponent 0.026 < s < 0.73 which predicts hopping of charge carriers. The bulk conductivity showed activation with temperature, significant values of activation energy are deduced and discussed. An average value of the energy gap width, 2.05 eV obtained using optical absorption in UV–visible spectra for PVA/CuI nanocomposite polymer electrolyte.