In this paper, we reported the preparation, characterization, and catalytic performance of TiO 2 doped with Mn for the selective oxidation of toluene to benzyl alcohol and benzaldehyde without any solvent. The structure of the catalyst was determined by X-ray diffraction (XRD), X-ray photoelectron spectroscopy (XPS), nitrogen adsorption-desorption analysis (Brunauer-Emmet-Teller [BET]), scanning electron microscope (SEM), transmission electron microscope (TEM), and mapping. The results demonstrated that the catalytic properties of Mn-TiO 2 were higher than those of pure Mn 3 O 4 and TiO 2 . The effects of reaction temperature, reaction time, oxygen pressure, and the amount of catalyst were studied. Under the optimal conditions, Mn-TiO 2 could afford 6.4% toluene conversion at a combined benzyl alcohol/benzaldehyde selectivity of 58.6%. Moreover, the catalyst can be repeated in the experiment for five times without significant loss of activity.