The electrochemical behavior of CCl4, CHCl3 and CH2O2 has been investigated by cyclic voltammetry at glassy carbon and silver electrodes in DMF+0.1 M Et4NClO4 in the absence and presence of a good proton donor. At both electrodes, each compound exhibits a series of reduction peaks which represent sequential hydrodechlorination steps up to methane. The nature of the electrode material and the proton availability of the medium affect drastically the voltammetric pattern of the compounds. Silver exhibits extraordinary electrocatalytic properties toward the reduction process,with positive shifts of the peak potentials of about 0.57-0.95V as compared to glassy carbon. Reduction of any polychloromethane, CHnCl(4-n) (n = 0-2), yields the carbanion CHnCl(3-n)- which partitions into two reaction channels: (i) protonation and (ii) Cl- elimination to give a carbene :CHnCl(2-n). If a strong proton donor is added into the solution, sequential hydrodechlorination becomes the principal reaction route at both electrodes. When, instead. purposely added acid is not present in solution, both reaction pathways ought to be considered. In these conditions, when possible, self-protonation reactions play an important role in the overall reduction process. (C) 2008 Elsevier Ltd. All rights reserved.