Zinc oxide (ZnO) and iron doped zinc oxide (Fe/ZnO) nanoflowers were successfully synthesized via a simple hydrothermal process. The samples were characterized by X-ray diffraction (XRD), X-ray photoelectron spectroscopy (XPS), Raman scattering, ultraviolet-visible (UV-vis) diffuse spectroscopy and scanning electron microscopy (SEM), and it was found that the dopant ions replaced some of the crystal lattice zinc ions, and furthermore, Fe3+ and Fe2+ ions coexist. Photocatalytic activities of the catalysts were assessed based on the degradation of rhodamine B (RhB) in aqueous solution under both UV and visible light irradiation (lambda > 420nm), respectively. All Fe/ZnO samples showed enhanced photocatalytic activity under the irradiation of visible light. On the contrary, Fe/ZnO products displayed poorer performance than that of pure ZnO in the presence of UV light. This phenomenon can be attributed to the coexistence of Fe3+ and Fe2+ in the ZnO host. The photophysical mechanism of the UV and visible photocatalytic activity was investigated with the help of surface photovoltage (SPV) and PL measurements, respectively. The results indicated the influence of coexistence of Fe3+ and Fe2+ in ZnO host on the separation and transfer behavior of the photogenerated charges in the UV and visible regions, which are distinctly different: under the irradiation of UV light, the recombination of the photogenerated electrons and holes was promoted, whereas the separation and transfer of photogenerated electrons and holes was facilitated under the visible light irradiation. The detailed photocatalytic mechanism and the role of Fe on the photodegradation process are discussed. (C) 2014 Elsevier B.V. All rights reserved.