Three different single crystals, Au(1 11), Au(332), and Au(33 1), were used as the substrate for palladium deposition in the underpotential deposition (UPD) regime. The Au(111) single crystal was used for control experiments to compare the behavior of the vicinal surfaces. Cyclic voltammetry in 0. 1 M sulfuric acid solution,as well as electrochemical impedance spectroscopy (EIS) were used to study the hydrogen adsorption on the Pd thin films. Our results suggest that the voltammetric peaks at similar to 0.3 V versus the reversible hydrogen electrode (RHE) are related to the adsorption of hydrogen at large palladium terraces, and that at least two adjacent Pd rows are needed in order for the adsorption to take place. Further cycling to more positive potentials leads to the oxidation and slow dissolution of the Pd film. The behavior of the oxidation cycles is explained in terms of a higher stability of Pd at the steps.