Vanadium　doped　titania　hollow　microspheres　were　successfully　prepared　using　polystyrene　latex　particles　as　template　and　using　organmetallic　Ti　(IV)　as　precursor.　The　resulting　samples　were　characterized　by　FT-IR,SEM,TEM,　XRD　and　UV-Vis　DRS.　The　results　show　that　the　morphology　of　titania　hollow　microspheres　do　not　exhibit　remarkable　change　when　adding　low　concentration　of　vanadium.　The　wall　thickness　of　these　hollow　microspheres　is　in　the　range　from　20nm　to　30nm.　The　vanadium　promotes　the　phase　transformation　of　TiO(2)　hollow　microsphere　from　anatase　to　rutile　phase.　With　increasing　concentration　of　vanadium,　the　adsorption　edge　of　as-prepared　titania　hollow　microspheres　show　stronger　absorbance　of　light　with　longer　wavelength.　The　moderately　vanadium　doped　titania　hollow　microspheres(1.0%)　exhibit　better　photocatalytic　activity　for　the　decomposition　of　methyl　orange　in　aqueous　solution.