The reductive dehalogenation of CCl4, CHCl3, CH2Cl2 and CH3Cl has been investigated by cyclic voltammetry and control led-potential electrolysis at Ag, glassy carbon (GC) and graphite electrodes in dimethylformamide (DMF) + 0.1 M Et4NClO4 in the absence and presence of a proton donor. in particular, the study was focused in the evaluation of the intermediates and final products of the reduction process and how their distribution could be affected by tuning relevant chemical and electrochemical parameters. In general, depending on the value of the applied potential, all polychloromethanes (PCMs) can be partially or completely dechlorinated, methane being exclusively formed in the latter case. The nature of the electrode material and the proton availability of the medium affect drastically the distribution of reduction products. The results point out that at both types of electrode, reduction of PCMs takes place through two competing reaction pathways both leading to methane. One reaction route involves a sequence of reductive dehalogenation steps, with the removal of one chlorine atom at a time, whereas the other is based on hydrogenolysis of carbenes and bypasses the intermediacy of partially dechlorinated PCMs. The presence of a proton source affects substantially the hydrodehalogenation efficiency, enhancing the concentration of intermediate PCMs and the final yield of methane. The silver electrode exhibits an extraordinary electrocatalytic effect resulting in remarkable positive shifts of the reduction potentials of all PCMs with respect to GC. The Ag surface strongly affects the kinetics of the dissociative electron transfer to CHnCl(4-n) (n = 0-3) as well as the reactivity of the intermediate radicals, carbanions and carbenes. (C) 2008 Elsevier B.V. All rights reserved.