The electrochemical oxidation of 4,4(')-biphenol (4BP) was studied by cyclic voltammetry in the absence and presence of 2-mercaptobenzimidazole (2MB) in aqueous/ethanol (50/50 v/v) mixture, to evaluate whether the electrogenerated 4,4(') -diphenoquinone (4BP(OX)) reacts with 2MB and determine the electrochemical oxidation pathway of 4BP in the presence of 2MB. The data show that the reaction of 4BP(OX) with 2MB can be accomplished in an undivided cell equipped with carbon anode and stainless steel cathode leads to the formation of 3-((lH-benzo[d]imidazol-2-yl)thio)-[l,l(')-biphenyl]-4,4(')-diol. This method has led to the development of a green, reagentless and facile galvanostatic method for the synthesis of 2-(phenylthio)-lH-benzo[d]imidazole derivatives. (C) 2018 Ihe Electrochemical Society.