The spontaneous catalytic transfer hydrogenation (CTH) was investigated using the H2PO2- ion as the H-donor, 3-buten-1-ol as the model organic molecule and a Pd-black film as the catalyst. A pre-evaluation of the competitive ability of the unsaturated alcohol and H-donor to co-adsorb on the surface was performed by cyclic voltammetric experiments. The performance of the CTH was characterized in terms of the reaction selectivity, H-donor efficiency, material yield, reactant conversion, reaction rate and catalyst stability in successive hydrogenation reactions. The effect of the H-donor concentration on these parameters was also analysed. Evidence was given for the modification of the surface catalyst during the course of the hydrogenation but no effect on the catalytic activity was observed. The prospective ability of this catalyst material to be precharged in a hypophosphite solution and to operate as a source of hydrogen for the catalytic hydrogenation was demonstrated. For comparison, the electrocatalytic hydrogenation was also studied using the same organic compound and catalytic material as in the CTH. (C) 2007 Elsevier B.V. All rights reserved.