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 microspheres 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 TiO₂ 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.