A novel samarium-doped spherical-like ZnO hierarchical nanostructure (Sm/ZnO) was synthesized via a facile and surfactant-free chemical solution route. The as-synthesized products were characterized by X-ray diffraction, Brunauer-Emmett-Teller surface area analysis, field emission scanning electron microscopy together with an energy dispersion X-ray spectrum analysis, transmission electron microscopy, UV-visible diffuse reflectance spectroscopy, and photoluminescence spectroscopy. The results revealed that Sm ion was successfully doped into ZnO. It was also observed that the Sm doping increased the visible light absorption ability of Sm/ZnO and a red shift for Sm/ZnO appeared when compared to pure ZnO. The photocatalytic studies revealed that the Sm/ZnO exhibited excellent photocatalytic degradation of 2,4-dichlorophenol (2,4-DCP) compared with the pure ZnO and commercial TiO2 under visible light irradiation. The photocatalytic enhancement of Sm/ZnO products was attributed to their high charge separation efficiency and (OH)-O-center dot generation ability as evidenced by the photoluminescence spectra. The photocatalytic investigation also showed that various parameters exerted their individual influence on the degradation rate of 2,4-DCP. By using a certain of radical scavengers, (OH)-O-center dot was determined to play a pivotal role for the 2,4-DCP degradation. Moreover, the Sm/ZnO could be easily separated and reused, indicating great potential for practical applications in environmental cleanup. (c) 2013 Elsevier Inc. All rights reserved.