Recently, some studies show various organic compounds such as pesticides and dyes degraded with the irradiation of ultraviolet light and visible light in the presence of oxalic acid and ferric ion (ferrioxalate/UVvis process). The process has much advance than other technologies because it can utilize the wavelength of 300∼450nm and also under the condition of neutral pH. Chlorinated organic compounds such as trichloroethene (TCE), which have caused ground water pollution on a lot of sites, have never been applied by photodegradation with this process. In this study, we showed the degradation of TCE in the presence of oxalic acid and iron ion and the change of pH, ferric and ferrous ion concentration during the photodegradation of TCE with ferrioxalate/UV-vis process. TCE was degraded in the presence of oxalic acid and iron ion. In the reactions, the equilibrium of oxalate ion and iron ion is important since it determines the amount of ferrioxalate complex which absorbs light and induces the reactions of the degradation of TCE. Thus, the pH value and iron ion concentration are the important factors which determine the amount of ferrioxalate complex. The pH is nearly constant during the photodegradation of TCE. The ferrous ion concentration was decreased as soon as beginning photodegradation of TCE, and then the ferrous ion concentration and ferric ion concentration became constant.