A Ce-Mn composite oxide possessing a rod-like morphology (with a fixed molar ratio of Ce/Mn=3:7) was synthesized through a hydrothermal method. Mn ions were doped into a CeO2 framework to replace Ce ions, thereby increasing the concentration of oxygen vacancies. The formation energies of O vacancies for the Ce-Mn composite oxide were calculated by applying density functional theory (DFT). The data showed that it was easier to form an O vacancy in the composite. The catalytic behavior of the Ce-Mn composite oxide for benzene degradation was researched in detail, which exhibited a higher activity than the pure phases. Based on this, the Ce-Mn composite oxide was chosen as a supporter to load PdO nanoparticles. The activity was enhanced further compared with that of the supporter alone (for the supporter, the reaction rate R-214 degrees C=0.68x10 (4) molg(cat) (1) s (1) and apparent activation energy E-a=12.75 kJ mol(-1); for the supporting catalyst, R-214 degrees C=1.46 x 10(-4) mol g(cat)(-1) s(-1), E-a=10.91 kJmol(-1)). The corresponding catalytic mechanism was studied through in situ Raman and FTIR spectroscopy, which indicated that the process of benzene oxidation was related to different types of oxygen species existing at the surface of the catalysts.