<p>Polyvinyl alcohol (PVA) and polyvinylpyrrolidone (PVP) were blended in 1:1 ratio and stand-alone films were produced through solution-casting technique. The polymer blend was incorporated with various concentrations of vanadium pentoxide (V₂O₅) nanofillers (0, 2, 4, 8, 12, and 16 wt.%). The structural changes brought by the nanofillers in the composite matrix were verified by FTIR and XRD analyses. Photoluminescence studies signify a maximum emission intensity at 4 wt.% V₂O₅, indicating a strong influence of this filler concentration on the luminescent behavior of the films. UV–Vis studies exhibited a systematic reduction in the optical bandgap with rise in nanofiller content. The nanocomposite films exhibit strong absorbance up to a wavelength of 550&#xa0;nm, indicating their potential use in optoelectronic devices, visible-light photodetectors, and solar-energy-harvesting applications. AFM images provided insight into the surface morphology, highlighting changes in roughness and texture due to filler incorporation. Dielectric studies demonstrated an increase in dielectric constant up to 12 wt.% filler loading, suggesting an optimum concentration for enhanced dielectric performance. A Universal Testing Machine (UTM) is used for mechanical testing, which verifies that adding V₂O₅ improves tensile strength and film stability. These results indicate PVA/PVP/V₂O₅ nanocomposite films are promising candidates for high-frequency electronic and dielectric device applications.</p>