Using a facile new synthesis method, the fabrication of cerium oxide doped birnessite MnO2 (delta-MnO2) catalysts has been operated, for the toluene catalytic combustion. These samples were investigated by XRD, Raman, TEM, BET, H-2-TPR and XPS techniques and their catalytic activities were investigated and compared. The catalytic combustion of toluene was investigated as the model reaction for VOCs abatement. The several CeO2/MnO2 based nano composites were accomplished via controlling the molar proportion of potassium permanganate and cerium acetate raw materials. The subtle CeO2 doped delta-MnO2 catalyst displayed better reducibility at lower reduction temperature, with the higher Mn4+/Mn3+ ratio, which converts completely the 1000 ppm toluene to CO2 and H2O at 318 degrees C and its T90 is 277 degrees C. The excellent catalytic performance of Mn12Ce1O(x) catalyst might be resulted from the synergistic effect between the highly dispersed CeO2 nanoparticles and the delta-MnO2 substrate at their interface. These new observations provide a new perspective on the design of the high activity catalyst for decomposing the volatile organic compounds (VOCs abatement).