A novel Fe-0/CeO2 composite was synthesized, characterized and applied for removal of different kinds of chlorophenols, including 4-chlorophenol (4-CP), 2,4-dichlorophenol (2,4-DCP), 2,4,6-trichlorophenol (2,4,6-TCP) and pentachlorophenol (PCP). Fe-0/CeO2 composite was prepared by the impregnation method, their physicochemical properties were characterized before and after reaction by X-ray diffraction (XRD), scanning electron microscopy (SEM) with energy-dispersive X-ray spectrometer (EDX), high-resolution transmission electron microscopy (HRTEM), the Brunauer-Emmett-Teller (BET) method, X-ray photoelectron spectroscopy (XPS), and Raman spectroscopy. The results showed that spherical zero-valent iron particles ranged in 200-400 nm were dispersed on ceria matrix. The BET surface area and pore volume of synthesized Fe-0/CeO2 composite were 16.76 m(2)/g and 0.056 cm(3)/g, respectively. The introduction of CeO2 facilitated the generation of chemisorbed oxygen on the surface and the dissolution of Fe-0. 2,4-DCP was adsorbed on the Fe-0/CeO2 surface, reductive dechlorinated by Fe-0 and Fe2+, and/or oxidative degraded by hydroxyl radicals ((OH)-O-center dot), superoxide radicals (O-2 radical anion), and H2O2 species. Additionally, the extent of chlorophenols removal, TOC removal and dechlorination followed the order of PCP > 2,4-DCP > 2,4,6-TCP > 4-CP. (c) 2013 Elsevier B.V. All rights reserved.