Electrochemical oxidation of catechols (1a-1c) has been studied in the presence of acetylacetone (3) as a nucleophile in aqueous solutions, using cyclic voltammetry and controlled-potential coulometry. The results indicate that the quinones derived from catechols (1a-1c) participate in Michael addition reactions with acetylacetone (3) to form the corresponding benzofurans (6a-6c). In this work we have proposed a mechanism for the electrode process. The electrochemical synthesis of benzofurans 6a-6c has been successfully performed at carbon rod electrodes and in an undivided cell. (C) 2003 Elsevier B.V. All rights reserved.