The photoelectrochemical oxidation of aniline on rutile form TiO2 film electrodes prepared by direct thermally oxidation of titanium sheet was studied both in single and double compartment photoreactor. The results showed that the rutile form of TiO2/Ti electrode had excellent photoactivity by applying anodic bias potential and irradiation simultaneously. Oxygen and its reduction products could accelerate the oxidation rate of aniline though its supply was not necessary in this system. The oxidation rate of aniline performed in single compartment cell was larger than that in double compartment cell under the conditions of either by nitrogen or air purging. The oxidation rate could be evaluated by the photocurrent, but it was dependent on the presence of oxygen. The photocurrent efficiency for aniline degradation was related to potential, pH, and single/double compartment cell. Total mineralization of aniline requires a much longer illumination time than its disappearance. (C) 2003 Elsevier B.V. All rights reserved.