A series of Ru-based mono and bimetallic materials were prepared and evaluated in the catalytic oxidation of chlorobenzene. Among the different Ru-based catalysts, 1Ru/TiO2(P25) was the most active catalyst and contributed the lowest complete oxidation temperature, suggesting that commercial P25 TiO2 was the best support for Ru catalysts. After ceria oxides were introduced into the Ru catalytic system, the catalytic activity of 1Ru-5Ce/TiO2(Rutile) dramatically improved and that of P25 supported catalysts was decreased. Comparing the chlorobenzene consumption rates for 1Ru/TiO2 and 1Ru-5Ce/TiO2 at 280 degrees C, it could be concluded that monometallic Ru catalytic system was appropriate for P25 support, and the Ru-Ce bimetallic catalytic system was suitable for the rutile TiO2 support. At 280 degrees C, for 1Ru-5Ce/TiO2(Rutile) and 1Ru-5Ce/TiO2(P25), the chlorobenzene conversion was stabilized at approximately 91% and 86%, respectively. According to the physicochemical properties of the catalysts as characterized by X-ray diffraction (XRD), X-ray photoelectron spectroscopy (XPS), transmission electron microscopy (TEM), high-angle annular dark-field scanning transmission electron microscopy (HAADF-STEM), and Hydrogen temperature programmed reduction (H-2-TPR), it can be concluded that (a) electrophilic O-ads species play an important role in VOCs oxidation; (b) abundant RuO2 nanoparticles on the surface of 1Ru-5Ce/TiO2(Rutile) result in higher catalytic activity and stability; and (c) dispersion is not the major factor for the catalytic activity, rather the unique structure greatly facilitated the catalytic activity and stability.