This work demonstrates the feasibility of utilizing arguably the most inert, least basic, and extremely weak coordinating carborane anions, [H-CB11X6Y5](-) (X = H, Cl, Br; Y = H or Me), as supporting electrolytes in low-polarity media. The redox behaviors of some model systems such as ferrocene (Fc), CoCp (CO)(2) and [(eta(6)-C6Me6)RhCp*](2+) in the presence of [NBu4][H-CB11H11], [NBu4][H-CB11Cl6Me5] and [NBu4][H-CB11Br6Me5] resemble those observed with other weakly coordinating anions (WCAs) such as [B(C6F5)(4)](-) and [Al(OC(CF3)(3))(4)](-). The overall results show that this class of carborane anions is a promising candidate for a new generation of WCA-based supporting electrolytes, for exploration the molecular electrochemistry of various organic, inorganic and organometallic compounds. (C) 2015 Elsevier B.V. All rights reserved.