In the present study, undoped and antimony (Sb) doped ZnO nanocrystals (NCs) were prepared by a simple and economical sol-gel method. X-ray diffraction (XRD) and transmission electron microscopy (TEM) revealed the purity of the obtained phase and its high crystallinity. Raman analysis confirms the hexagonal Wurtzite ZnO structure. According to the diffuse reflectance results, the band gap was found to decrease up to 3% of Sb doping (ZSb3 sample). The results of X-ray photoelectron spectroscopy (XPS) measurements reveal that Sb ions occupied both Zn and interstitials sites. The successful substitution of antimony in ZnO lattice suggests the formation of the complex (Sb-zn-2V(zn)) acceptor level above the valence band. Particularly for ZSb3 sample, the UV photoluminescence (PL) band presents an obvious red-shift attributed to the formation of this complex. Rhodamine B (RhB) was used to evaluate the photo catalytic activity of Sb-doped ZnO NCs under sunlight irradiation. It was found that oxygen vacancies play a major role in the photocatalytic process by trapping the excited electrons and inhibiting the radiative recombination. During the photocatalytic mechanism, the Sb doping, expressed through the apparition of the (Sb-zn-2V(zn)) correspondent acceptor level, enhances the sunlight absorption within the ZnO band gap, which stimulates the generation of hydroxyl radicals and promotes the photocatalytics reaction rates. Such important contribution of the hydroxyl radicals was confirmed experimentally when using ethanol as scavenger in the photocatalytic reaction. The photodegradation experiments reveal that ZSb3 sample exhibits the highest photocatalytic activity among all the prepared samples and presents a good cycling stability and reusability. The influence of the initial pH in the photodegradation efficiency was also monitored and discussed. (C) 2016 Elsevier B.V. All rights reserved.