In this work, the role of chloro-species generated during the electrolysis of Rhodamine B (RhB) solutions containing chloride and perchlorate salts as supporting electrolytes was studied. Likewise, the effect of light irradiation in the activation of the oxidants is also evaluated. To do this, essays of electrolysis, photoelectrolysis, and chemical oxidation in the presence of light with the oxidant generated electrochemically were carried out. Results showed that RhB was effectively oxidized by electro-irradiated techniques. Color removal is faster than chemical oxygen demand (COD) and total organic carbon (TOC) removal, due to the rapid attack of chromophore group of the molecule. In general, light irradiation has a positive effect during the electrolysis of RhB at high current densities. In chloride media, light irradiation seems to favor the decomposition of hypochlorite produced. The effect of light irradiation is explained in terms of the activation of oxidants in the bulk of the electrolytic treatment by production of highly efficient radicals. Results of chemical oxidation essays may indicate that UV light irradiation has not a clear catalytic influence out of an electrolytic environment. The findings presented in this communication are described and discussed in the light of the existing literature. (C) 2015 Elsevier B.V. All rights reserved.