Electrochemical synthesis of new acetaminophen derivatives (4a-4c) has been carried out by the electrochemical oxidation of acetaminophen, N-(4-hydroxyphenyl)acetamide, in the presence of arylsulfinic acids (3a-3c) as nucleophiles in aqueous solution using cyclic voltammetry. The results revealed that the electrochemically generated N-acetyl-p-benzoquinone-imine (2) participates in Michael type addition reaction with arylsulfinic acids via an EC mechanism and is converted to the acetaminophen derivatives (4a-4c). The present work has led to the development of a facile and environmentally friendly reagent-less electrochemical method with high atom economy and safe waste under green conditions. (C) 2013 The Electrochemical Society. All rights reserved.