In the context of the electrocatalytic hydrogenation (ECH) process of unsaturated organic molecules, we have shown using infrared spectroscopy and water contact angle measurements that catalysts powders made of palladium oil conductive tin dioxide (10% Pd/SnO2:F) and on alumina (10% Pd/Al2O3) are functionalized with organic chains when they were dipped in supporting electrolyte aqueous solutions containing different carboxylic acids. The carboxylic acids are bound to the supports (SnO2:F and Al2O3) through either the carboxyl or carboxylate groups. The measurement of contact angles confirmed that the support surface is functionalized by the carboxylic acids but also indicated the hydrophobic or hydrophilic character of the resultant surface. With these functionalized catalysts, the effectiveness of electrocatalytic hydrogenation of phenol could be modulated by controlling the adsorption of phenol. The adsorption depends mainly on the functionalization agent (carboxylic acid) and to a lesser extent on the identity of the support material (SnO2:F or Al2O3). Because adsorption is the step that induces the selectivity of the ECH process, controlling this phenomenon by functionalizing the catalyst support in Situ is promising for obtaining molecules of choice.