The electrochemical reactions of 2 mM benzyl alcohol (BA) on platinum and palladium electrodes in 0.1 M HClO4 were studied by means of differential electrochemical mass spectrometry (DEMS) and cyclic voltammetry. The objective of this work is to investigate the influence of electrode nature on the reactivity of BA. On-line mass spectroscopy analysis of volatile products reveals that the interaction of BA with these metals partially occurs dissociatively producing benzene. CO2 is the sole oxidation product detected. The corresponding mass signal exhibits three different contributions. The extent of each contribution is found to depend strongly on the electrode nature, though in the case of palladium, it also varies with changes in the electrode potential range covered during the voltammetric scan. The different catalytic activity of platinum and palladium is demonstrated during the electroreduction process. Both hydrogenolysis of the molecule and hydrogenation of the aromatic ring occur on platinum, whereas the latest process is of little significance on palladium. (C) 2000 Elsevier Science Ltd. All rights reserved.