Mn-doped CeO2 and CeO2 with the same morphology (nanofiber and nanocube) were synthesized through hydrothermal method respectively. When applied to benzene oxidation, the catalytic properties of Mn-doped CeO2 were higher than those of CeO2, which was related with the concentration of O vacancy. Compared to CeO2 with the same morphology, more oxygen vacancies were formed on the surface of Mn-doped CeO2, due to Mn ion replacing Ce ion. The lattice replacement was analyzed through XRD, Raman, electron energy loss spectroscopy and electron paramagnetic resonance technology. The formation energies of oxygen vacancy on the different exposed crystal planes [(110) and (100)] for Mn-doped CeO2 were calculated by applying the density functional theory (DFT). The data showed that the oxygen vacancy was easier to be formed on the (110) plane. The factors influencing catalytic behavior were elaborated, which indicated that surface oxygen vacancy played an important part in catalytic reaction.