Several palladium-based electrocatalysts dispersed onto a Vulcan XC-72 carbon support (Pd/C, PdxAu1-x/C and PdxPt1-x/C) were prepared by the "water-in-oil" microemulsion method and characterized by physicochemical methods (TEM, HRTEM, EDX, XRD, etc.). The electrochemical activity of these catalysts towards the electro-oxidation of formic acid was investigated by cyclic voltammetry, and compared to that obtained with the monometallic catalysts. The electrochemical decomposition of formic acid in a PEMEC at relatively low cell voltages (0.2-0.7 V for a current density of 100 mA cm(-2) according to the catalyst used) was performed with a much lower electrical energy (1.2-1.6 kWh(Nm(3) H-2)(-1) compared to that necessary for water electrolysis (similar to 5 kWh(Nm(3) H-2)(-1), Formic acid has been chosen as a model compound with the lowest decomposition energy (Delta H similar to 32 kJ mole(-1)) compared to that needed for water decomposition (Delta H similar to 286 kJ mole(-1)). It has been demonstrated that this technology may allow saving at least two thirds of the electrical energy needed by the classical water electrolysis technology for producing pure hydrogen. Moreover the use of platinum free Pd-based catalysts for the anodic oxidation of formic acid leads to high reaction rates at relatively lower overvoltages, i.e. 0.2-0.4 V at 100 mA cm(-2). (C) 2011 Elsevier Ltd. All rights reserved.