The laponite pillared by the CeO2 modified TiO2 (Ce-Ti-lap) were prepared by microwave intercalation reaction with laponite as the layered clay, tetrabutyl titanate and cerium chloride as the Ce-Ti composite pillaring agent, and characterized by X-ray diffraction (XRD), scanning electron microscopy (SEM) and Brumauer-Emmett-Teller (BET) surface area. The photocatalytic activities of Ce-Ti-lap were investigated by the degradation of methyl orange (MO). The results showed that Ce and Ti could be introduced to the interlayers of laponite, and the CeO2 modified TiO2 pillared structures could be formed with the basal spacing and the BET surface area of Ce-Ti-lap significantly increased. The Ce-Ti-lap showed the best photocatalytic activity in the degradation of MO compared with the pure TiO2, the laponite only pillared by TiO2 (Ti-lap) and the laponite only pillared by CeO2 (Ce-lap). Using the Ce-Ti-lap with the mass fraction of Ce/Ti (X-Ce) of 0.05, under the conditions of the initial concentration of MO 20 mg/L, irradiation time 120 min, pH value 4, photocatalyst dosage 1.5 g/L, the decoloring rate of MO achieved 96.3%, which decreased only 3.9% after being used 5 times, indicating that the Ce-Ti-lap had excellent photocatalytic activity and active stability.