Nanostructured titanium oxide films were deposited on silicon substrate via sol-gel dip coating method with tetrabutyl titanate as precursor. With reflective spectroscopic ellipsometry, the ellipsometric parameters Ψ and Δ of TiO2 films were measured. Then, with the Cauchy model, the ellipsometric data were fitted, and both the thickness and the optical constants at 380—800 nm wavelength of the films were obtained. A comparison was made between the reflectance of the films derived with the spectrophotometer and the simulated results. Meanwhile, the thickness of the films was calculated by interference method. Moreover, with the atomic force microscopy the surface microstructures of the films annealed at different temperatures were observed, and the relationship between the surface microstructures and optical constants of films was further discussed. The results showed that Cauchy model works well in describing the dispersion relationship of the TiO2 films, and the variation rules of optical constants (the refractive index, the extinction coefficient) with wavelength were obtained. The optical constants of the films were related with the microstructure. Those simulated reflectance spectrum accorded well with the measured result. And with a deviation of only 25%, the calculated value of the thickness was in accordance with which was obtained by spectroscopic ellipsometry.