A novel buoyant Ce-TiO 2 /V 2 O 5 photocatalyst was prepared by a sol-gel method. Titanium tetrapropoxide and vanadium pentoxide were employed as precursor. Cerium ions were used as dopant and hollow micron-sized glass microspheres were used as support. The surface morphology and microstructure of anchored photocatalyst were characterized by using scan electron microscope, energy dispersive spectra and X-ray diffraction patterns. It was showed that the anchored TiO 2 consisted of mixed crystalline phase of anatase and rutile. The Ce-TiO 2 /V 2 O 5 film appeared uniform, smooth and has good adherence to hollow microsphere. Photoactivity of the anchored catalyst on microsphere under ultraviolet irradiation was compared with catalyst powder and anchored catalyst on glass slice by degradation of methyl orange solution. The results showed that the catalyst-microsphere exhibited similar activity to powder catalyst, and exhibited higher activity than catalyst-glass slice. The degradation efficiency of methyl orange solution by catalyst-microsphere reached almost 99% after 70 min run, while the degradation efficiency by catalyst-glass slice was only 45%. The adsorption ability of catalyst on microsphere was higher than catalyst on glass slice and powder catalyst due to the high special surface. After laid for adsorption-desorption processes for 6 h, the concentration of methyl orange reduced 42.2% by microsphere catalyst while the concentration reduced 31% by powder catalyst, and the concentration reduced only 4.15% by slice catalyst. The high special surface area and buoyant property of microsphere-catalyst make a greater exposure both to the light source and to the pollutants, which are favorable for photocatalysis.