This study delineates the process of fabricating and the results of investigating the dielectric properties of hybrid particles created through the integration of Poly(vinylidene fluoride) (PVDF) filled with RuO2 coated on BaTiO3 nanoparticles (nBT), designated as RuO2–nBT. These hybrid particles were successfully synthesized employing a simple and cost–effective solid–state reaction method. The inclusion of RuO2–nBT in the PVDF matrix engendered a notable enhancement in its dielectric properties. Notably, a RuO2–nBT fraction of 0.5 manifested a dielectric constant (ε') of 107.4 and a dielectric loss tangent (tanδ) value of 0.062 at 30 C and 1 kHz. These findings signify the effective role of interfacial polarization occurring between the PVDF matrix and the RuO2–nBT hybrid particles, leading to a marked improvement in dielectric attributes. Moreover, the observed low tanδ value indicates the elimination of conductive pathways, an inhibitory effect attributed to the incorporation of RuO2–nBT hybrid particles. This study underscores the promising potential of RuO2–nBT hybrid particles in fine–tuning and augmenting the dielectric properties of polymer composites, particularly in scenarios necessitating low tanδ and high ε' values.