An overall comparative study was carried out on N-doped, F-doped, and N–F-codoped TiO 2 powders (NTO, FTO, NFTO) synthesized by spray pyrolysis in order to elucidate the origin of their visible-light-driven photocatalysis. The comparisons in their experimentally obtained characteristics were based on the analysis of XPS, UV–Vis, PL, NH 3-TPD and ESR spectra. The comparisons in their theoretically predicted properties were based on the analysis of the calculated electronic structures. As the results, N-doping into TiO 2 resulted in not only the improvement in visible-light absorption but also the creation of surface oxygen vacancies. F-doping produced several beneficial effects including the creation of surface oxygen vacancies, the enhancement of surface acidity and the increase of Ti 3+ ions. Doped N atoms formed a localized energy state above the valence band of TiO 2, whereas doped F atoms themselves had no influence on the band structure. The photocatalytic tests indicated that the NFTO demonstrated the highest visible-light activity for decompositions of both acetaldehyde and trichloroethylene. This high activity was ascribed to a synergetic consequence of several beneficial effects induced by the N–F-codoping.