Palladium-polypyrrole nanostructured composite films can be easily synthesised using a two-step procedure comprising the electrochemical synthesis of palladium nanoparticles (Pd-NPs) that are subsequently po ten tio statically deposited onto a polypyrrole thin film electrosynthesised from an acetonitrile solution. The composite thin films have good conductivity and their transmission electron micrographs show that the metallic inclusions have a mean diameter of about 5 nm with a homogeneous size distribution. X-ray photoelectron spectroscopy (XPS) analysis reveals the presence of two surface oxidation states for the as-synthesised Pd-NPs as well as for those deposited on the films. On the basis of experimental findings, a structural model for the Pd-NPs is proposed.