The degradation of 2,4-dichlorophenol (2,4-DCP) by the photo-Fenton-like (Fe3+/H2O2/UVC) process under various reaction conditions was investigated. It was interesting to find that the reaction kinetics of 2,4-DCP in Fe3+/H2O2/UVC systems varied depending on the initial [Fe3+] concentration. A pseudo first-order kinetic and a non-conventional kinetic were discovered at low and higher [Fe3+] concentrations, respectively. A model was used to simulate the non-conventional kinetic process, where two character parameters (the initial decay rate and the final decay fraction) were found to be critical in determining the process. The two parameters successfully quantify the photo-Fenton-like oxidation under different concentrations of [Fe3+] and [H2O2] and the corresponding ratios of Fc(III)/H2O2. The reaction intermediates were identified by an LOMS analysis and a reaction mechanism was proposed. © 2005 Elsevier B.V. All rights reserved.