Titania/organically modified silane hybrid thin films for photonic applications were prepared by combining a low temperature sol-gel technique and a spin-coating process from an organic-inorganic hybrid system. Effects of the titanium content and heat treatment temperature on the structural and optical properties of the hybrid thin films were characterized by atomic force microscopy and UV-visible spectroscopy. It is found that the optical and microstructural properties of the hybrid thin films depend on the heat-treatment temperature and titanium molar contents. The thickness and the refractive index of the hybrid thin films were also measured and found to be related to the heat treatment temperature and titanium molar content. These results indicate that a dense and high transparent hybrid thin film can be obtained at a low heat treatment temperature. Potential photonic device structural patterns can easily fabricated from the as-prepared hybrid thin films by using etching process.