Mesoporous cobalt-doped TiO2 (Co-TiO2) material has been synthesized by solid-state reaction route. The textural properties of the samples are monitored by the X-ray diffraction (XRD), high resolution transmission electron microscopy (HRTEM) and energy dispersive spectroscopy(EDS), Raman spectroscopy, N2-physisorption, Fourier transform infrared spectroscopy (FT-IR), ultraviolet visible light spectroscopy (UV-Vis) and X-ray photoelectron spectroscopy(XPS). It is shown that the mesoporous Co-TiO2 is consisted of polycrystalline with some amorphous mixture and trace cobalt oxide. Cobalt has been incorporated into the framework of anatase TiO2. The bending vibration at 1124 cm-1 of Co-O-Ti bond in mesoporous Co-TiO2 material is confirmed. Interestingly, it possesses a large BET surface area (97.6 m2/g) and a narrow distribution of pore size presenting a better photocatalytic reactivity for toluene oxidation. Within 150 min irradiation, the maximum conversion (95 mol%) of toluene oxidation is obtained.