Palladium-nickel/titanium (Pd-Ni/Ti) and palladium-nickel/polymeric pyrrole film/titanium (Pd-Ni/PPy/Ti) electrodes were prepared by electrochemical deposition. The electrochemical characteristics of the Pd-Ni/Ti and Pd-Ni/PPy/Ti electrodes were Studied by means of cyclic voltammetry (CV) based on orthogonal experiments. CV studies on the electrodes were conducted in 0.5 mol/L sulfuric acid solution. Experimental results indicate that the hydrogen adsorption peak value of the Pd-Ni/PPy/Ti electrode seen at ca. -500 mV is larger than that of Pd-Ni/Ti electrode. Scanning electron microscope (SEM) images indicate that polymeric pyrrole film, which formed on electrode can modify the electrode surface configuration significantly and provide the surface of the Pd-Ni/PPy/Ti electrode with more layers and a larger surface area.