In this work, Sm-doped ZnO was prepared by a Sol-Gel method. The structure, morphology, composition and optical properties of the prepared samples were investigated by X-ray diffraction (XRD), scanning electron microscope (SEM), energy dispersive spectroscopy (EDS), surface photovoltage spectrum (SPS) and X-ray photoelectron spectroscopy (XPS). Sm-doping results in high specific surface area and boosted photogenerated carriers separation efficiency, and produces more active free radicals to participate in the photocatalytic reaction. Photocatalytic activities of the samples toward removal of rhodamine B(RhB) were evaluated under UV light irradiation, the results display that Sm-doped ZnO shows higher photocatalytic activity than the reference ZnO.