A novel reaction system consisted of a supported TiO 2 film electrode, a Ru Ti oxide film electrode and air (oxygen) electrode is reported. The air (oxygen) electrode can provide H 2O 2 continuously for homogeneous photochemical oxidation reaction on the spot. In this reactor, degradation reaction of aniline occur from interface of TiO 2 film to all solution which is irradiated by ultraviolet ray. The degradation rate of aniline was characterized by measuring the change of chemical oxygen demand (COD) in solution under different conditions. It was found that the degradation rate of aniline in the novel system increased apparently as compared with single heterogeneous photocatalysis and homogeneous photochemistry system. It can be explained in terms of combining acts of heterogeneous photocatalysis and homogeneous photochemistry. A novel reaction system consisted of a supported TiO 2 film electrode, a Ru Ti oxide film electrode and air (oxygen) electrode is reported. The air (oxygen) electrode can provide H 2 O 2 continuously for homogeneous photochemical oxidation reaction on the spot. In this reactor, degradation reaction of aniline occur from interface of TiO 2 film to all solution which is irradiated by ultraviolet ray. The degradation rate of aniline was characterized by measuring the change of chemical oxygen demand (COD) in solution under different conditions. found that the degradation rate of aniline in the novel system increased apparently as compared with single heterogeneous photocatalysis and homogeneous photochemistry system. It can be explained in terms of combining acts of heterogeneous photocatalysis and homogeneous photochemistry.