The natural vanadiferous rutile was modified by heating, quenching and electron irradiation, and the different photoactivities of samples under different treatments were studied. XRD patterns of all samples reveal that all the treatments fail to result in new phases or any phase transition. In the IR spectra, there is a broad band at about 3400 cm -1 in non-modified, heating and quenching samples, which is attributed to the stretching vibrations of OH groups. The IR spectrum of the irradiated sample, however, shows no above_mentioned band. XPS (X-ray Photoelectron Spectroscopy) was used to study the change of chemical characteristics on the sample surfaces. The concentrations of oxygen and vanadium atoms increase with heating and quenching. This may be related to the increase of defects on the surface, which will add active sites for adsorption of water and hydroxyl groups. Accordingly, the photoactivities of these samples are distinctly improved. Unfortunately, electron irradiation fails to accelerate the photoactivity; on the contrary, it even somewhat slows down the process due to the reduction of adsorbed water and hydroxyl groups.