Abstract The radiolytic degradation of methyl tert-butyl ether (MTBE) in air-equilibrated dilute solution was investigated. Complete degradation of MTBE can be achieved within 5 min of irradiation at 59.7 Gy/min. The observed first-order degradation rate constant, called dose constant, increased from 0.04 to 0.56 Gy −1 as the concentration of MTBE decreased from 92500 to 19 μg/L. Tert-butyl formate, tert-butyl alcohol, acetone and methyl acetate were found to be the primary intermediates of the degradation reaction with yields of 47%, 11%, 6.4% and 9.1%, respectively. The degradation of MTBE or its intermediates was also found to depend on the concentrations of benzene and cupric ion. The study shows that the removal of MTBE can be significantly decreased with increasing concentration of benzene. Little affects were observed with the presence of cupric ions, while the degradation of TBF was apparently reduced. These results indicate that gamma radiolysis can be a potentially effective treatment for the removal of MTBE in contaminated water systems.