To evaluate the effects of different TiO₂ crystalline phases on the catalytic oxidation performance of benzene on Pt-loaded TiO₂ catalysts, physicochemical examinations were conducted using several spectroscopic and analytical techniques. Obvious effects on the valence state and morphology of Pt were exhibited by different crystalline phases. The rutile phase favored the formation of specific Pt(111) crystal faces, which enhanced the amount of surface-active oxygen species. Moreover, the àPt-O-Ti species was formed between Pt⁴⁺ and Ti at the edge of the Pt nanoparticles, promoting both electron flow and the transfer of reactive oxygen species, thus accounting for catalytic activity.