Radiation treatment in the presence of catalysts such as anatase, P25 and bentonite showed efficient removal of TCE (trichloroethylene) and PCE (perchloroethylene) compared with gamma-irradiation alone. Gamma-ray pretreatment of P25 and bentonite enhanced the decomposition of TCE and PCE, respectively. The change in the catalysts by gamma-rays was characterized by their EPR spectra. For anatase and bentonite, the peaks in the spectra increased significantly, and the pattern of the spectra changed in the case of P25. The relationship between the peaks and pollutant decomposition should be further clarified due to the complexity of the spectra.