Cerium (Ce)-doped tungsten oxide nanostructures have been generated by using a simple solvothermal method with cerium chloride salts and tungsten hexachloride as precursors. The as-synthesized samples were characterized by electron microscopy, x-ray diffraction and x-ray photoelectron spectrometry. The photocatalytic activities of the samples were evaluated by degradation of methyl orange in an aqueous solution under visible light irradiation. Results showed that the as-synthesized samples underwent morphological evolution with decreasing W/Ce molar ratio, from one-dimensional bundled nanowires through straighter, shorter and thicker bundled nanorods to two-dimensional bundled blocks, then to a mixture of bundled nanorods and agglomerated nanoparticles, and finally to particle agglomerates. The Ce-doped tungsten oxides exhibited better photocatalytic activities than that of the undoped tungsten oxide. The cerium-doped tungsten oxide bundled blocks synthesized with a W/Ce molar ratio of 15:1 possessed the most effective photocatalytic activity among the tested samples. These novel nanomaterials may find potential applications as visible-light-driven photocatalysts.