With the objective to investigate the influence of zinc oxide-cerium oxide (ZnO-Ce2O3) nanoparticles on the electrical properties of polyvinyl alcohol (PVA), PVA/ZnO-Ce2O3 nanocomposite films were prepared by solution intercalation method with different weight percentage viz., 0.5, 1.0, and 2.0 wt% of ZnO-Ce2O3 nanoparticles. The fabricated nanocomposites were characterized by Fourier transform-infrared spectroscopy (FT-IR), X-ray diffraction (XRD), and differential scanning calorimetry (DSC). The effect of ZnO-Ce2O3 nanoparticles on the dielectric constant (epsilon'), dielectric loss (epsilon aEuro(3)), electric modulus (M' and MaEuro(3)), ac conductivity (sigma (ac)), and dielectric loss tangent (tan delta) over a range of frequencies at room temperature of PVA nanocomposites have been studied. FT-IR, XRD, and DSC analysis indicates the nature of ZnO-Ce2O3 nanoparticles interaction with the PVA matrix. The morphological behavior of the nanocomposites has been performed using scanning electron microscopy (SEM). The dielectric behaviors such as dielectric constant (epsilon') and dielectric loss (epsilon aEuro(3)) increases with increase in nanoparticle concentration, but decreases with increase in frequency. But, the electric modulus (M') increases with increase in frequency. Dielectric loss tangent (tan delta) decreases with increase in filler content at lower frequency, but at higher frequencies the tan delta increases with increase in nanoparticles content. AC conductivity (sigma (ac)) of PVA/ZnO-Ce2O3 nanocomposites increases with increasing frequency following the universal dielectric response law.