With sol-gel processing and rapid thermal annealing (RTA), crack-free PbTiO3 and PbZr1−xTixO3(x=0.2-0.8) ferroelectric thin films were prepared on Si(100) and Pt/Ti/SiO2/Si(100) substrates respectively. Results from x-ray diffraction (XRD) show that the films are single perovskite phase structure. Scanning electron microscopy (SEM) was used to determine the grain sizes of the thin films. Energy dispersive spectroscopy (EDS) of x rays was used to analyze the composition of the films. From infrared reflection spectroscopy in the wavelength region of 40-700 cm−1 at 300K, the vibrational mode frequencies in PbTiO3 thin films on silicon substrates were obtained at the wavenumbers of 79, 155, 206, 298, 344, 461, 520 and 621 cm−1. Among these phonon modes, the modes at 298 and 461 cm−1 have not been reported before. The infrared optical constants and the thickness of PZT thin films on Pt/Ti/SiO2/Si(100) substrates were directly measured in the wavelength region of 2-12μm by an automatic wavelength swept infrared spectroscopic ellipsometer. These constants include: refractive index (n), extinction coefficient (k), thickness of the films and absorption coefficient (α). Possible correlation among the processing, microstructure and optical properties of the thin films were discussed.