The reduction of tert-butyl peracetate, lauryl peroxide and dibenzoyl peroxide has been investigated at platinum and glassy carbon electrodes in DMF. It is known from the studies of Maran et al. that peroxides reduction mechanisms generally involve at first a slow electron transfer concerted with the scission of the peroxide bond. Then the radical produced at the electrode is immediately reduced, which leads to a two electrons consumption. Similar results were obtained in this study for tert-butyl peracetate, lauryl peroxide and dibenzoyl peroxide. Besides, the determination of the number of electrons involved in the reduction at different time scales gave a number of two for lauryl peroxide, dibenzoyl peroxide, tert-butyl peroxybenzoate and di-tert-butyl peroxide and showed that this transfer is followed, in the case of tert-butyl peracetate, by a subsequent chemical reaction consuming a part of the substrate. (C) 2005 Elsevier Ltd. All rights reserved.