The present study demonstrates the effectiveness of an electrochemical treatment consisting in cycles of constant potential oxidation and reduction of polycrystalline palladium surface in the enhancement of the electro-oxidation of ethanol, ethylene glycol and glycerol. The rise of the activity after the treatment has been ascribed to the increase of both surface area and density of low coordination surface atoms. FTIR spectra showed that a change in the reaction products distribution also occurs, resulting, in some cases, in an increased tendency to cleave the C-C bond. (C) 2013 Elsevier B.V. All rights reserved.