In recent years, titanium dioxide has received ever growing interest, thanks to its promising applications in numerous fields such as environmental remediation, H2 generation and photovoltaics. Here, transparent and mechanically robust TiO2 films are deposited by a simple and inexpensive electrochemically assisted procedure on various kinds of substrates, both conductive and nonconductive (e.g., glass slides or different metal laminas with variable surface roughness). The obtained films are uniform, crack-free and exhibit excellent chemical, mechanical, and electrochemical robustness. The obtained layers are compared to films prepared by a routine preparation technique, such as dip coating, showing much better morphological, optical, and conductive properties. The photo-activity of TiO2 can be exploited to obtain transparent spectroelectrochemical systems and to control the wetting features of the surface. Applications concerning the modulation of the wettability are presented with respect to both the antifogging and antistain properties. The photoelectrochemical properties of TiO2 films are exploited to activate a photoelectrochemical polymerization of polypyrrole onto an unconductive support. These materials are promising for numerous applications such as smart windows, antifogging mirrors, solar cells, and optically transparent electrodes.