Cordierite-supported three-dimensionally ordered macroporous (3DOM) and nanoparticle La0.8Ce0.2MnO3 catalysts were prepared by PMMA-templating and impregnation methods, respectively, to eliminate toluene in low temperature. The catalysts were characterized by BET, SEM, HRTEM, XRD, H-2-TPR, NH3-TPD and XPS. The effects of calcination temperature and morphology on the specific surface area, pore volume and size, crystal phase, reduction ability, surface acid distribution and surface property were investigated, and then toluene removal efficiency and apparent active energy were also studied. The results show that the structure and morphology of the active component have a great influence on the specific surface area of the catalyst. At the same calcination temperature of 600 degrees C, the specific surface area of 3DOM La0.8Ce0.2MnO3/cordierite is 35.3m(2).g(-1), which is much larger than that of the nanoparticle La0.8Ce0.2MnO3/cordierite (11.9m(2).g(-1)). Calcination temperature also can affect the properties of the catalyst and catalytic combustion performance. With different calcination temperatures of 600, 700 and 800 degrees C, the 3DOM sample calcinated at 600 degrees C (T-50= 147 degrees C, (T90) = 217 degrees C, and E-a = 27.01 kJ.mol(-1); SV= 6000 h(-1)) showed the best performances in reduction property, specific surface area, adsorption oxygen concentration, and catalytic combustion performance.