A series of CeaMnOx hollow microsphere like arbutus with hierarchical structure are prepared by redox co-precipitation method and applied for catalytic toluene combustion. The Ce0.03MnOx,, shows a better catalytic performance for toluene combustion with high stability, water resistance, even under the condition of 5vol.% H2O. The results of XRF, XRD, Raman, N-2 adsorption-desorption, SEM, TEM prove that the doping of Ce can affect the structure of Ce-a/InOx. such as much smaller particle size and higher specific surface area. The characterizations of H-2-TPR, O-2-TPD, XPS certify the strong interaction between Ce and Mn oxides that leads to more surface adsorbed oxygen and Me4+ species due to oxidation reduction cycle of Mn3+ + Ce4+ Mn4+ + CO+ after Ce addition. Meanwhile, the Toluene-TPD in different conditions confirms the introduction of water promoted the catalytic oxidation of toluene. In situ DRIFTS is used to investigate the reaction process of toluene oxidation. And the results reveal that the Ce0.03MnOx catalyst has much stronger ability to adsorb and activate toluene compared with MnO. catalyst, especially under with H2O. That may be the main reason that the Ce0.03MnOx catalyst exhibits the special catalytic activity for toluene combustion.