Three-dimensional (3D) ordered and wormhole-like MoO3 mesoporous structures were synthesized based on ultrasound-assisted vacuum impregnation method. Carbon template was used in the synthesis process, which was prepared by using mesoporous molecular sieve KIT-6. Hexaammonium molybdate acted as molybdenum source. The as-prepared MoO3 samples were characterized by transmission electron microscope (TEM), X-ray diffraction (XRD), thermogravimetric analysis/differenctial scanning calorimetry (TG/DSC), and N-2 adsorption-desorption measurement. The catalytic performance of MoO3 mesoporous structure was evaluated by hydrogen temperature-programmed reduction (H-2-TPR), and complete oxidation of toluene and carbon monoxide (CO). It was found that the initiation temperatures of toluene were 203 degrees C, 215 degrees C and 225r, respectively, and the initiation temperatures of CO were 114 degrees C, 158 degrees C and 180 degrees C, respectively, with their conversion rates of 50%, 90% and 100%, respectively. The well catalytic performance was attributed to 3D ordered mesoporous structure and high surface area of as-obtained MoO3 materials.