<p>Composite films of polyvinylidene fluoride–barium tungstate (PVDF-BaWO₄) were created through the solution casting method, wherein ceramic powder was integrated into the PVDF polymer matrix. The synthesized films underwent structural, morphological, and electrical characterization. The vibrational spectroscopy illustrates the enhancement of electroactive <i>β</i> phase F(<i>β</i>) of the polymer. In the frequency range of 100&#xa0;Hz to 1&#xa0;MHz, the dielectric constant of the composite increases with the rise in filler concentrations. The PVDF film loaded with 0.9 wt% BaWO₄ filler exhibits the highest dielectric constant, attributed to the smaller size of the filler and their homogeneous and discrete dispersion in the matrix. In-depth examination of electrical attributes with impedance spectroscopy unveils the respective influences of grains and grain boundaries on the resistive and capacitive properties of the composite. The study of frequency-dependent electrical conductivity at various temperatures suggests the applicability of Jonscher’s power law supports the transport properties of the composites. The observed low electrical conductivity, high dielectric constant, and low loss indicate the potential use of PVDF/BWO composites in developing optoelectronics and capacitive energy storage devices.</p>