Winery wastewater is characterized by high organic content consisting of alcohols, acids and recalcitrant high-molecular-weight compounds (e.g. polyphenols, tannins and lignins). So far, biological treatment constitutes the best available technology for such effluents that are characterized by high seasonal variability; however the strict legislation applied on the reclamation and reuse of wastewaters for irrigation purposes introduces the need for further treatment of the bioresistant fraction of winery effluents. In this context, the use of alternative treatment technologies, aiming to mineralize or transform refractory molecules into others which could be further biodegraded, is a matter of great concern. In this study, a winery effluent that had already been treated in a sequencing batch reactor was subjected to further purification by homogeneous and heterogeneous solar Fenton oxidation processes. The effect of various operating variables such as catalyst and oxidant concentration, initial pH, temperature and lamp power on the abatement of chemical oxygen demand (COD), dissolved organic carbon (DOC), color, total phenolics and ecotoxicity has been assessed in the homogeneous solar Fenton process. In addition, a comparative assessment between homogeneous and heterogeneous solar Fenton processes was performed. In the present study the homogeneous solar Fenton process has been demonstrated to be the most effective process, yielding COD, DOC and total phenolics removal of about 69%, 48% and 71% in 120 min of the photocatalytic treatment, respectively.