The crystalline structure analysis, dielectric and piezoelectric properties of neat PVDF, PZT and PZT/PVDF film composites with different volume fractions (0.15, 0.3, 0.45, 0.6, 0.75) of PZT prepared by solvent casting and subjected to poling procedures have been investigated by employing X-ray fluorescence, X-ray diffraction, Fourier transformation Infrared, Capacitance Measuring Circuit, LCR, and optical microscopy coupled with mathematical modeling of dielectric and piezoelectric constants.