The electrocatalytic reduction of tert-butyl hydroperoxide and cumyl hydroperoxide at platinum and glassy carbon disc microelectrodes has been investigated in N,N-dimethylformamide and 1,2-dichloroethane in the presence of a small amount of iron (III) chloride in the solution. In the course of a negative scan, metallic iron was electrodeposited on the electrode, making possible the reduction of the hydroperoxide at the electrode surface. During the repetitions of the recordings, an unusual reproducibility of the reduction signal was observed. This reproducibility is due to an in situ reconstitution of the active surface of the electrode that allows the electrode reaction to take place, at each scan, on a clean non-contaminated new electrode surface. (C) 2004 Elsevier B.V. All rights reserved.