Evidence is presented that copper, silver, and their alloys with palladium, may display an exceptional reactivity in the contact of alpha,omega-alkanes [Br-(CH(2))(n)-Br]. Thus, the use of coppered surfaces as cathode materials shows a spectacular potential shift (Delta E approximate to 1 V) for the main reduction step when compared to glassy carbon taken as a standard interface. Such cathodic reactions are particularly easy and fast with 1,3-dibromopropane (DB3). Thus, it is expected that a preliminarily transient [(CH(2))(3)Cu((II)),2Br(-)] monomer or polymer, is formed: the indirect reduction by use of 3D electrodes from copper powder in suspension may produce at electrified surfaces (made of glassy carbon, platinum, or nickel) fine deposits of copper nano-particles. Oppositely, silver (essentially by means of Ag-Pd alloy employed as cathode material) reacts with each C-Br bond and the observed cathodic behaviour is uniform with all alpha,omega-alkanes. A special attention is drawn on the nature of modified surfaces and the enhancement of catalysis kinetics brought by the use of copperized and silverized electrodes. (C) 2009 Elsevier B.V. All rights reserved.