The electrochemical reduction of benzyl halides PhCH2X (X = Cl, Br and I) has been investigated at Ag and glassy carbon (GC) electrodes in CH3CN + 0.1 M Et4NClO4. At both electrodes reduction of PhCH2X involves irreversible electron transfer concerted with breaking of the carbon-halogen bond. All three halides exhibit a single 2e(-) reduction peak at GC, whereas up to three peaks can be observed at the Ag electrode. Silver exhibits remarkable catalytic properties for the reduction process, which is positively shifted by 0.45-0.72 V with respect to GC. The mechanism of reduction of the organic halides at Ag involves adsorption of both the starting reagents and their reduction products. Adsorption of PhCH2Cl and PhCH2Br is weak and slow, whereas PhCH2I is more rapidly and strongly adsorbed, so that two distinct peaks can be observed for the reduction of the dissolved and adsorbed molecules. Controlled-potential electrolyses at Ag have shown that the process may be directed to the production of bibenzyl or toluene, depending on the applied potential. (c) 2006 Elsevier Ltd. All rights reserved.