A palladiated copper (Cu-Pd) interface of well-defined structure is formed by dipping a metallic copper substrate in solutions of palladium sulphate in 0.1 N sulphuric acid. Copper is quasi-immediately covered with a shiny metallic surface, which was characterized as corresponding to a CuPd phase dispersed at the copper interface in nanoparticles. This modified surface was successfully used as a new cathode in the field of bond cleavage reactions, in particular those of the carbon-iodide and carbon-bromide bonds. The accent is put on the potential shift between the use of a regular glassy carbon surface and this particular palladiated interface; the potential shift is so large that it enables the one-electron cleavage of C-I and C-Br bonds probably because transient free alkyl radicals are not electro-active at the potential at which the first electron transfer occurs. (c) 2006 Elsevier B.V. All rights reserved.