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.