Na doped ZnO nanocrystals (NCs) were successfully produced by sol-gel process and characterized by X-ray diffraction (XRD), transmission electron microscopy (TEM), high resolution TEM (HRTEM), Raman scattering, UV-vis diffuse reflectance spectroscopy and photoluminescence (PL). XRD analysis indicated that all the prepared samples present pure hexagonal wurtzite structure without any Na related phases. The lattice distortion, calculated using Williamson hall equation, induces stress and a reduction of NCs size from 71.4 to 24.5 nm. TEM images showed NCs with hexagonal shape and a rather uniform size distribution. The selected area electron diffraction (SAED) patterns confirmed the high crystal quality along the (101) direction and is consistent with the hexagonal wurtzite structure of ZnO. The Raman spectra are dominated by E-2(high) mode of ZnO. High Na doping shows the occurrence of anomalous local vibrational Raman modes close to 270 and 513 cm(-1) that are related to intrinsic host lattice defects and distortion, respectively. Optical band gap was found to vary with Na content. Photoluminescence (PL) spectra indicate the presence of a high density of defects in ZnO NCs which are mainly oxygen vacancies. Finally, the obtained NCs were used as a photocatalyst to degrade Rhodamine B (RhB) in solution, under solar irradiation. Na doping enhances the photocatalytic activity of ZnO NCs till an optimum concentration of 0.5% where a full degradation was observed after 120 min of sun light irradiation. Furthermore, this sample presents a good cycling stability and reusability. Based on scavangers test, it was found that both superoxide and hydroxyl oxidizing radicals are mainly actives. (C) 2016 Elsevier B.V. All rights reserved.