The ultrathin films with nanometre control over thickness and multilayered structures of polypyrrole (PPY) were manufactured by in-situ self-assembled technique. A controlled thickness of PPY was deposited on polyanion, poly(styrene sulfonate) (PSS) surfaces as a function of time; previously PSS had been deposited on various substrates (glass, mica, indium-tin-oxide coated glass plates). Later, alternate PPY and PSS films were fabricated on such substrates by the layer-by-layer technique. The films were characterized by using UV-visible, electrochemical and Quartz Crystal Microbalance techniques. The resulting morphology of the manufactured films was investigated by Atomic Force and the Scanning Tunneling Microscopies. The electrochemical surveying of self-assembled PPY films in different electrolytic media highlighted the sensor application. Typical supramolecular films of PPY/PSS were found to have conductivity values in the range of 10(-2)-10(-1) S/cm.