Titania dioxide (TiO2) layers were synthesized via the acid-catalysed sol-gel route using titania (IV) ethoxide, and then annealed at temperatures varying in the range of 150–700 °C. The research concerned the effect of annealing temperature on the structure of TiO2 layers, their surface morphology, and their optical properties. Further, X-ray diffractometry, and Raman spectroscopy were used to determine the structure of TiO2 layers. Scanning electron and atomic force microscopy were used to study the surface morphology of TiO2 layers. Transmittance, reflectance, absorption edge, and optical homogeneity were investigated by UV-VIS spectrophotometry, while the refractive index and thicknesses of TiO2 layers were measured using a monochromatic ellipsometer. Chromatic dispersion characteristics of the complex refractive index were determined using spectroscopic ellipsometry. Structural studies have shown that the TiO2 layers annealed at temperatures up to 300 °C are amorphous, while those annealed at temperatures exceeding 300 °C are polycrystalline containing only anatase nanocrystals with sizes increasing from 6 to 20 nm with the increase of the annealing temperature. Investigations on the surface morphology of TiO2 layers have shown that the surface roughness increases with the increase in annealing temperature. Spectrophotometric investigations have shown that TiO2 layers are homogeneous and the width of the indirect optical band gap varies with annealing temperature from 3.53 eV to 3.73 eV.