This work aims to prepare LiZnVO4 nanoparticles and incorporate them into PVDF as a host polymeric material using the casting method for rechargeable Li-battery applications. The effect of LiZnVO4 on the structural and optical properties of the samples was studied using XRD, FT-IR, and UV-is techniques. Moreover, the electrical conductivity of the prepared films was studied. The XRD spectra show the semicrystalline structure of PVDF and the rhombohedral structure of LiZnVO4. Scherer's equation was used to determine the crystallite size of LiZnVO4 which is nearly 83 nm. The interaction between PVDF and LiZnVO4 was approved by shifting some FT-IR bands. The band gap energies were decreased by increasing LiZnVO4 due to the density in the localized states in the mobility band gap in PVDF. The AC parameters as a function of frequency and temperature were investigated in detail. Both ε' and ε" had their maximum values at low frequencies and decreased as the frequency and temperature increased. The XRD and FT-IR findings corroborate the increased dielectric characteristics and tan δ at 5 wt. percent LiZnVO4, suggesting their potential use as a basic material in the development of cutting-edge energy storage devices and lithium-ion batteries.