Solution casting method is used to prepare solid polymer electrolyte films composed of Na2TeO3/PVA (x wt% of Na2TeO3; x = (0.0, 1.1, 3.3, 4.4, 8.9 and 17.8). The description of crystalline nature parameters of the solid polymer electrolyte films has been confirmed by adding salt by XRD analysis. The average inter-crystallite separation and stacking fault is reduced as the dislocation density increments with a rising salt concentration in the polymer matrix. The decrease in the indirect optical energy gap and the observed increase in refractive index (n) of Na2TeO3/PVA samples with the increasing Na2TeO3 salt compared with the pure PVA suggest the possibility of their use in optical device applications. Moreover, the materials' refractive index values were determined from Moss, Reddy, Anani, and Kumar-Singh relationships. In terms of equivalent circuits, the impedance spectra were fitted and explained. The optical limiting of prepared films with different salt content was investigated by continuous laser beam waves operated at 532.8 nm. The findings showed that the films attenuate the laser beam. The obtained dielectric parameters supposed that the Na2TeO3 salt embedded within the PVA as a matrix conveys faster charge transfer and acts as a non-ideal capacitor. The conductivity–frequency dependence was investigated using empirical Jonscher’s power law. The produced polymeric electrolyte films can be widely relevant to electronic and optoelectronic, and biomedical applications.