The catalytic oxidation of toluene has been investigated over pure CeO2 hierarchical catalyst for the first time. The novel CeO2 catalyst was prepared by a hydrothermal-driven assembly method. The structure of CeO2 catalyst was consisted of nanowire self-assembled hierarchical microspheres. The new hierarchical CeO2 catalyst showed much better catalytic activity than analogous nonporous catalyst by traditional hydrothermal method. The hierarchical CeO2 catalyst could reach more than 90% toluene conversion even as low as 210 degrees C (T-90) under a high space velocity of 60,000 mL/(g.h). The high catalytic activities could be attributed to the large surface areas, in addition, the hierarchical porous structures provide more contents of surface oxygen vacancies for the dissociation of gaseous O-2 on the surface.