Novel triarylamine (Ar3N) mediators bearing an ionic-tag moiety were synthesized from 4,4-dibromotriphenylamine. Their electrochemical properties were investigated by cyclic voltammetry both in organic solvent and ionic liquid HF salt. The electrocatalytic reactions such as deprotection and fluorodesulfurization of dithioacetals were successfully carried out using these Ar3N mediators in an undivided cell at room temperature. (C) 2012 Elsevier Ltd. All rights reserved.