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Ce-doped TiO2-multi walled carbon nanotubes (Ce-doped MCNTs/TiO2) composites were successfully synthesized by the hydrothermal method. The crystalline structure, surface morphology and optical properties of samples were characterized using X-ray diffraction (XRD), transmission electron microscope (TEM) and ultraviolet-visible diffuse reflection spectroscopy (UV-vis) analysis technologies. The Ce-doped TiO2 particles of anatase type were well dispersed on the MCNTs surface. Compared with pure TiO2, the absorption of Ce-doped MCNTs/TiO2 composites in the visible region increased by 19.4% and had a red shift about 30 nm. The photocatalytic activity of Ce-doped MCNTs/TiO2 composites was investigated by the photodegradation of methyl orange (MO) in the sunlight and compared with that of un-doping MCNTs/TiO2. 1.0% Ce doping could effectively improve the photocatalytic activity of MCNTs/TiO2 and the degradation rate for the MO reached 82.85% after irradiated 5h in the sunlight.