A fluorous micellar system in water has been created to produce a large interfacial area between these media that retains substrates, effectively facilitating intermolecular Diels-Alder reactions due to repulsion effects from both media. Because LiFOS functioned not only as a surfactant but also as a supporting electrolyte, an electrochemical approach could be introduced to evaluate the rate acceleration effects. The measurement of the particle size distribution of the fluorous micelles clearly supported these evaluations. (C) 2011 Elsevier Ltd. All rights reserved.