Abstract Chlorophenols were selected for this study because most of them are toxic and difficult to biodegrade. They represent a particular group of priority toxic pollutants listed by the US EPA in the Clean Water Act and by the European Decision 2455/2001/EC. The efficiency of advanced oxidation processes for degradation of chlorophenols has been extensively documented. The catalytic wet hydrogen peroxide oxidation process, involving oxidation with H2O2 and solid catalysts in mild reaction conditions, was found to be very attractive for different pollutants; however, data regarding the degradation of chlorophenols are very scarce. The aims of this paper were: (i) to prepare and characterize a series of iron-exchanged montmorillonites and (ii) to assess their catalytic performances in a Fenton-like process for the oxidation of para-chlorophenol. DR-UV-VIS spectroscopy was tentatively used to elucidate the structure of the iron oxo sites intervening in the reaction. This approach has been used previously for ion-exchanged zeolites and was able to distinguish between isolated Fe(III) species and FexOy clusters of different nuclearity. The catalytic tests, performed at room temperature, showed that all iron-containing clays were very active, leading to the complete oxidation of parachlorophenol and a significant reduction of TOC values. 4-chlorocatechol was the major reaction intermediate found in the CWHPO of 4-CP, followed by hydroquinone and traces of benzoquinone, 5-chloro-1,2,4-benzenetriol, 1,2,4-benzenetriol and 3- chloro-muconic acid. The leaching test indicates that the catalytic activity is mainly due to leached iron ions, at least in the second part of the process.