Highly ordered mesoporous Co3O4 nanostructures were prepared using SBA-15 silica as hard templates. The mesoporous structures were characterized by X-ray diffraction, high resolution transmission electron microscopy, and N2 adsorption/desorption isotherm analysis. The results demonstrated that the as-prepared mesoporous Co3O4 has an ordered P6mm symmetric mesoporous structure. The optical absorption properties of the mesoporous Co3O4 were investigatted by UV-Vis spectroscopy and the results indicate that the mesoporous Co3O4 materials are semiconducting with direct band gaps of 2, 1.385 and 0.38 eV. The gas-sensing performance of the mesoporous Co3O4 was tested towards a series of typical solvents. They demonstrated a good sensing performance towards these vapour with rapid response and high sensitivity at low operating temperature.