The electrochemically-induced Stevens rearrangement of 2-(benzyldimethyl)ammonium acetophenone has been investigated by in situ UV-vis spectroelectrochemistry. Voltammetric analysis and absorption spectra recorded during the potentiostatic reduction indicate that the reaction proceeds via a one-electron transfer with a Platinum cathode and generation of an ammonium ylide intermediate. (C) 2013 Elsevier Ltd. All rights reserved.