Potassium ferrate [Fe(VI)] is a promising oxidant widely used in water treatment for the elimination of organic pollutants. In this work, the reaction kinetics, products, and mechanisms of the antimicrobial agent chlorophene (CP) undergoing Fe(VI) oxidation in aqueous solutions were investigated. CP is very readily degraded by Fe(VI), with the apparent second-order rate constant, k, being 423.2 M-1 s-1 at pH 8.0. A total of 22 oxidation products were identified using liquid chromatography-quadrupole time-of-flight-mass spectrometry , and their structures were further elucidated using tandem mass spectrometry. According to the extracted peak areas in mass spectra, the main reaction products were the coupling products (dimers, trimers, and tetramers) that formed via single-electron coupling. Theoretical calculations demonstrated that hydrogen abstraction should easily occur at the hydroxyl group to produce reactive CP· radicals for subsequent polymerization. Cleavage of the C-C bridge bond, electrophilic substitution, hydroxylation, ring opening, and decarboxylation were also observed during the Fe(VI) oxidation process. In addition, the degradation of CP by Fe(VI) was also effective in real waters, which provides a basis for potential applications.