A strategy for the synthesis of sol-gel hybrid materials that contain perfluorocyclobutyl groups is reported. Sol-gel films have been prepared from three types of siloxane monomers using a typical sol-gel method in an acidic atmosphere, followed by UV irradiation and dimerization. The materials show high thermal stability that exceeds 400 degrees C. At a wavelength of 1550 nm, the refractive index, the bire-fringence, and the optical loss of the sol-gel materials are found to be in the ranges of 1.4568-1.4876, -0.0003-0.0029, and 0.34-0.45 dB (.) cm(-1) respectively.