The ferroelectric (Pb, La) (Zr,Ti)03 (PLZT(9.4/65/35)) optical waveguiding thin films have been prepared on SiO2 coated Si and on silica glass substrates by pulsed laser deposition. X-ray θ–2θ scans revealed that the films are single-phase pseudo-cubic perovskite. The surface chemical composition of the as grown films were determined by XPS. The ferroelectric properties of the films as grown on Pt/Ti coated silicon were demonstrated by using a modified Sawyer-Tower circuit, and the optical waveguiding properties of the films were characterized by using a rutile prism coupling method. The as grown films have an average transmittance of 80% in the wavelength range of 400˜2000nm and a refractive index of 2.2 at 632.8mn close to the bulk PLZT. The distinct m-lines of the guided TM and TE modes of the films as grown on SiO2 coated Si substrates have been observed.