TiO2 films prepared by sol−gel route are active photocatalysts for the oxidation of organics in photoelectrochemical cells. The as-grown films for photocatalysis applications and those exposed to Ar+ or H2++Ar+ ion bombardment are characterized by different spectroscopic methods, such as X-ray diffraction (XRD), atomic force microscopy (AFM), UV−vis transmittance, photothermal deflection spectroscopy (PDS) and X-ray photoelectron spectroscopy (XPS), as well as by conductance. This material has defects associated with oxygen vacancies produced during the sample preparation which support nondissociative adsorption of O2 when films are exposed to air. Charge transfer from reduced Ti species to adsorbed dioxygen leads to Ti−O2- surface complexes that are partially removed by heating at 200 °C, and fully removed after 30 min ion bombardment. By comparison with the relatively well-understood structural defects of bombarded TiO2 we arise to a quite complete structural model of the as grown material which corresp...