Three rhodamine derivatives exhibiting electrofluorochromic properties were investigated by cyclic voltammetry and UV-Vis/fluorescence spectroelectrochemistry. Rhodamine 101 (Rh101, compound 1) was used as a reference model. In compound 2, the carboxylate anion of Rh101 was replaced by an alkyne moiety to allow further functionalization. The compound 3 was prepared from 2 by conversion of the alkyne to a triazole group bearing an alkyl chain with an alcohol function. These three rhodamine derivatives exhibited similar electrochemical behaviors. Their mono-electronic reductions produced the corresponding radical species which were stable on the time-scale of cyclic voltammetry. Additional reduction of electrogenerated radicals produced unstable anions which underwent subsequent chemical reaction, most likely protonation. Based on cyclic voltammetry investigations, absorption and fluorescence spectroelectrochemistry were then performed on compounds 1, 2, 3 and their parent reduced radicals 1a, 2a, 3a. UV-Vis spectroelectrochemistry, combined with TD-DFT calculation, confirmed the formation of radicals upon mono-electronic reduction of starting rhodamines. Fluorescence spectroelectrochemistry showed that, contrary to their parent molecules, electrogenerated radicals were non-fluorescent. Electrochemical fluorescence extinction was successfully achieved with all studied compounds. Moreover, compound 1 underwent on/off switching between fluorescent and non-fluorescent states repeatedly. Also, recovery of fluorescence in compound 3 was observed, which open interesting opportunities for the development of versatile rhodamine-based probes. (C) 2017 The Authors. Published by Elsevier Ltd. This is an open access article under the CC BY-NC-ND license (http://creativecommons.org/licenses/by-nc-nd/4.0/).