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Nanostructured PbZr0.52Ti0.48O3 (PZT) powder was synthesized at 500 °C-800 °C using sol-gel route. X-ray diffraction and Rietveld analysis confirmed the formation of perovskite structure. The sample heat treated at 800 °C alone showed the formation of morphotropic phase boundary with coexistence of tetragonal and rhombohedral phase. The PZT powder and PVDF were used in 0-3 connectivity to form the PZT/PVDF composite film using solvent casting method. The composite films containing 10%, 50%, 70% and 80% volume fraction of PZT in PVDF were fabricated. The XRD spectra validated that the PZT structure remains unaltered in the composites and was not affected by the presence of PVDF. The scanning electron microscopy images show good degree of dispersion of PZT in PVDF matrix and the formation of pores at higher PZT loading. The quantitative analysis of elements and their composition were confirmed from energy dispersive X-ray analysis. The optical band gap of the PVDF film is 3.3 eV and the band gap decreased with increase in volume fraction of PZT fillers. The FTIR spectra showed the bands corresponding to different phases of PVDF (α, β, γ) and perovskite phase of PZT. The thermogravimetric analysis showed that PZT/PVDF composite films showed better thermal stability than the pure PVDF film and hydrophobicity. The dielectric constant was measured at frequency ranging from 1 Hz to 6 MHz and for temperature ranging from room temperature to 150 °C. The composite with 50% PZT filler loading shows the maximum dielectric constant at the studied frequency and temperature range with flexibility.