Catalysts with ordered mesoporous structure usually behave superior in total oxidation of toluene. However, the link between reaction route and ordered mesoporous structure is still not fully founded currently. In this work, Co3O4 is selected as a model catalyst to illustrate the reaction route. The inter-mediates in the oxidation of toluene were analyzed via in situ Fourier transform infrared spectroscopy (in situ FTIR), high performance liquid chromatography (HPLC) and temperature programmed oxidation (TPO) experiment. Here we prove benzoquinone route as a special reaction route only observed in ordered mesoporous Co3O4, coexisting with the commonly reported benzoate route. Benzoquinone route is favored especially at lower temperature, accelerating the reaction rate, and acts as a crucial intrinsic reason for the better performance of ordered mesoporous Co3O4. The results also indicate that the activity of Co3O4 for oxidation of toluene depends on the quantity and nucleophilicity of surface oxygen species, which could be increased by the irregular surface morphology and the introduction of sodium. (C) 2017 Published by Elsevier B.V.