The microstructure and optical properties of TiO2 thin films, prepared by the sol-gel dip coating technique on glass substrates, were inspected. After deposition, the films were annealed at several temperatures in the 400–850 °C range and the resulting nanostructured films were studied by different techniques showing that their structural and optical characteristics evolved significantly with the increased annealing temperature. The analysis of these results by the assumption of the Tauc Lorenz model and the use of Wemple–DiDomenico equation leads to a correlation between microstructural aspects and optical characteristics of the films. Thus, crystallization processes (nucleation, growth and phase transformation) and the evolution of films texture and thickness with increasing annealing temperatures are related with the variation of the refractive index, average gap and extinction coefficient during annealing. Finally, the free-carrier concentration in the films, estimated from the Spitzer–Fan model, ranged from 1.44 × 1019 cm−3 to 3.07 × 1019 cm−3 with the changing annealing temperature, which is in agreement with those obtained in similar anatase thin films from electrical measurement techniques.