Europium-doped ZnO hierarchical micro/nanospheres (Eu/ZnO) were synthesized for the first time via a facile and surfactant-free chemical solution route. The as-synthesized products were characterized by X-ray diffraction, field-emission scanning electron microscopy, energy dispersion X-ray analysis, transmission electron microscopy, high-resolution transmission electron microscopy, X-ray photoelectron spectroscopy, UV-visible diffuse reflectance spectroscopy, nitrogen adsorption-desorption and photoluminescence spectroscopy. The results showed that the as-synthesized products were well-crystalline and accumulated by large amount of interleaving nanosheets. It was also observed that the Eu doping increased the light absorption ability of Eu/ZnO and a red shift for Eu/ZnO appeared when compared to pure ZnO. Under natural sunlight irradiation, the Eu/ZnO exhibited much higher photocatalytic activity than those of pure ZnO, Eu-doped ZnO nanorods (Eu/ZNRs) and commercial TiO2 for the degradation of phenol. The photocatalytic enhancement of Eu/ZnO products was attributed to their high charge separation efficiency and hydroxyl radical generation ability as evidenced by the photoluminescence spectra. By using several radical scavengers, hydroxyl radical was determined to play a pivotal role for the phenol degradation. Furthermore, the Eu/ZnO could be easily separated and reused, showing great potential for practical applications in environmental cleanup and solar energy conversion. (C) 2013 Elsevier B.V. All rights reserved.