The Sodium Molybdenum Oxide powders incorporating effect on the crystal structure, optical and dielectric characterization of NA-MOAT-04-C.2HYD/PolVA polymeric composite electrolyte films have been investigated. The samples were successfully synthesized by the simple casting method. Structural XRD measurements demonstrate that the density of the dislocation calculated using W-H plot and stacking energy fault simultaneously decreases in the PolVA polymer matrix with the adding NA-MOAT-04-C.2HYD content. The results revealed that the NA-MOAT-04-C.2HYD doping has a significant effect on the optoelectrical properties. The 7.4 wt% and 18.5 wt% NA-MOAT-04-C.2HYD were found to be the optimal conditions for the UV shielding applications. Such optoelectrical parameters tuned NA-MOAT-04-C.2HYD/PolVA polymeric composite electrolyte films are the promising materials for electro-optics, for the selection of alternative high-κ dielectric and nano-electronic devices. AC impedance results are compared to predictions of the appropriate electrical equivalent circuit parameters, which infers that the prepared systems are potential candidates for dielectric applications.