The acid-promoted disproportionation of 2,2,6,6-tetramethylpiperidinyl-1-oxyl (TEMPO) was studied in order to elucidate the recycling process of the catalytic oxidation of alcohol by nitroxides. Potentiometry, cyclic and hydrodynamic voltammetries with a rotating disk electrode (RDE) have been used to investigate the formation of a nitrosonium cation and a hydroxylamine by disproportionation of nitroxides in acetonitrile. The addition of p-toluenesulfonic acid caused the rest potential of the TEMPO/ nitrosonium cation couple to shift in a more positive direction and decreased the peak current in the cyclic voltammograms. The subsequent addition of 2,6-lutidine as a Lewis base made the rest potential and the peak current recover. These phenomena corresponded to the recycling of the catalytic process by TEMPO in a basic aprotic solution. (C) 2003 Elsevier Science Ltd. All rights reserved.