Electrochemistry of eight different boron clusters based on 12-vertex icosahedral framework has been studied in water-based electrolytes. This study revealed dependence of the electrochemical behavior on particular exo-skeletal substitution as well as on differences between previously studied divalent clos-o-dodecaborate anion and monovalent [CB11H12](-) anion. Electrochemical response of the latter ion retains the potential of that of the dodecaborate anion, but its relative intensity is considerably lower. Presence of two carbon atoms in parent neutral closo-1,2- and 1,7-dicarbaborane (ortho- and metacarborane) and their respective hydroxyderivative caused a shift of the electrochemical potential to lower values and higher peak sizes than for [CB11H12](-) anion. Most promising behavior for analytical determination in water-based interfaces was found for clusters substituted by OH group. (C) 2014 Elsevier B.V. All rights reserved.