Specific sol-gel formulations and protocols have been adapted to the fine patterning of TiO2 films using a very simplified UVA three-step lithography method. Mechanisms occurring during the photo-patterning procedure and a post-patterning thermal treatment have been studied by Fourier transform infrared spectroscopy, atomic force microscopy, X-ray diffraction, and ellipsometry. Discussions are proposed to support the influence of the photo-patterning procedure and post-patterning treatment on the shape and the dimension of so-formed microstructures. Original additional functionalities arising from such structures are also presented.