The degradation of 4-chlorophenol (4-CP) by using gamma rays generated by a 60 Co source in the presence of O 3 was investigated. The radiolysis of 4-CP and the kinetics of 4-CP mineralization were analyzed based on the determination of total organic carbon (TOC). The influence of initial 4-CP concentration and the free radicals scavengers (such as NaHCO 3 and t-butanol) on the 4-CP degradation was also studied. The results showed that when the radiation rate was 336 Gy·min −1 , 4-chlorophenol at concentration of 10 mg·L −1 could be completely degraded at the radiation dose of 2 kGy. The degradation of 4-chlorophenol could be described by a first-order reaction model, the rate constant of 4-CP degradation by combined ozonation and radiation was 0.1016 min −1 , which was 2.4 times higher than the sum of radiation (0.0294 min −1 ) and ozonation (0.0137 min −1 ). It revealed that the combination of radiation and ozonation resulted in synergistic effect, which can remarkably increase the degradation efficiency of 4-CP.