Natural rutile TiO2 shows photocatalysis on degrading trichloroethylene and tetrachloroethylene. In natural rutile, V, Fe, Cu, etc. substitute for Ti, resulting in lattice distortions and defects. We found that rutile, after heating, quenching and electron irradiation, changes its surface characteristics and photoactivity. The quenched rutile has the highest concentrations of adsorbed water and V on its surface, resulting in high photoactivity. For example, quenching at 1273 and 1373 K significantly improved photoactivity of rutile. The heated rutile also increased the concentration of adsorption water on the surface, e.g., rutile heated to 1273 K improved degradation rate of halohydrocarbons. On the contrary, electron irradiation decreased the concentration of adsorbed water on the rutile's surface, which results in lower degradation rate for trichloroethylene. Therefore, heating and quenching over 1237 K improve the photocatalytic efficiency of the natural V-bearing rutile on degrading halohydrocarbons. The XRD spectra of the rutile samples showed that heating, quenching and electron irradiation did not result in formation of new phases or phase transitions. (C) 2004 Elsevier B.V. All rights reserved.