A Cu-doped Fe-pillared Tunisian clay (Cu/Fe–PILC) was synthesized and used as a catalyst in the heterogeneous photo-Fenton oxidation of phenol in aqueous solution. Textural, structural and chemical characterization pointed to successful pillaring and incorporation of the Cu active phase. Photo-Fenton experiments proved the high activity of the Cu/Fe–PILC catalyst, which was able to completely mineralize the phenol present in the treated solution after a reaction time of 40min and in the presence of UV-C light. Moreover, the catalytic activity was not influenced by the pH of the initial phenol solution, over a wide range of pH from 3 to 7. An optimal dosage of H₂O₂ and of the catalyst was found. Phenol degradation was found to be slower in the presence of UV-A irradiation, needing longer reaction times. Negligible metal leaching and catalyst reutilization without noticeable loss of activity point to an excellent catalytic stability for this Cu/Fe–PILC catalyst.