Palladium is a preeminent material for the preparation of sensors for hydrogen and hydrogen-evolving compounds. Conducting polyaniline can be chemically or electrochemically functionalized by the incorporation of palladium clusters. Different interfaces in a three-dimensional matrix for hydrogen adsorption, desorption, and evolution were synthesized and characterized. Dispersions of palladium clusters in the polymer film were formed by various preparation routes, which can be classified as one- or two-step processes. In the one-step process, the composite material was obtained during the electrosynthesis of polyaniline film. In the two-step processes, Pd aggregated into the polyaniline modified electrode. Electrochemical examination, x-ray photoelectron spectroscopy, and Auger electron spectroscopy have been employed to characterize the composite materials in view of the hydrogen sorption and evolution as well as the binding energy state and the spatial distribution of the palladium clusters in polyaniline film.