The electrochemical reduction of tert-butyl hydroperoxide has been investigated in dimethylformamide and 1,2-dichloroethane. Voltammograms at platinum or at glassy carbon electrodes were indistinguishable from the background, whereas at iron electrodes a well-defined cathodic peak was observed. The electrocatalytic reduction of tert-butyl hydroperoxide was enhanced at freshly electrodeposited iron. A study of the reduction mechanism at iron electrode showed that both the electron transfer and the cleavage of the peroxidic bond occurred in a single step, consuming two electrons per mole with the production of tert-butanol. The electrocatalytic effect of iron was also observed for the cumyl hydroperoxide reduction. Organic peroxides are not implicated in an electrocatalytic reduction at iron surfaces. (C) 2004 Elsevier Ltd. All rights reserved.