The removal efficiency of 4-chlorophenol by ozonation was studied, and the reaction mechanism and characteristic of ozonation of 4-chlorophenol were investigated. Ozone and hydroxyl radicals are two strong oxidants during the process of ozonation. The experimental results showed that when there was no scavenger to inhibit OH· radicals, an intermediate product, hydrogen peroxide was formed during the ozonation of 4-chlorophenol. Hydrogen peroxide reacted with ozone at neutral pH and produced hydroxyl radicals. Ozone at the dosage of 113 mg/L could remove 20 mg/L4-chlorophenol and 39% TOC. With the complete inhibition of hydroxyl radicals, molecular ozone could effectively destroy 4-chlorophenol to form 4-quinone, which was subsequently oxidized to formic acid and oxalic acid. Two reaction pathways of the degradation of 4-chlorophenol by ozone and O3/OH· were proposed in this study. Ozonation is an effective method for reducing 4-chlorophenol,and has potential to practical application.