Method of electrostatic layer-by-layer assembly is used for preparation of the ultra thin functional films based on anionic complex of poly-3.4-ethylene dioxythiophene (PEDOT) — polystyrene sulfoacid (PSS) on the surface of the transparent indium-tin-oxide substrates. For the first time N-cetyl pyridinium chloride (CPC) was used as a cationic surfactant. It has been shown that nanofilms obtained in the presence of CPC demonstrate the optical properties and electrochemical behavior similar to PEDOT-PSS functional films that promises their application in electrochromic devices.