The formation of organic thin films by controlled-potential electrolysis (oxidation) of an aqueous solution containing surfactants with ferrocenyl moiety and an organic compound incorporated in micelles or in a dispersed organic pigment with use of the surfactants is examined. Opaque films of five azo dyes, vinylcarbazole, cetyl alcohol, dioctadecyldimethylammonium chloride, and 4,4'-didodecylviologen are formed through the former mechanism. Transparent films of phthalocyanine compounds (MPc (M = H2, Cu)), four halogen derivatives of CuPc, three perylene derivatives, and two quinones are formed through the latter mechanism. The scanning electron micrograph studies show that crystal size of the film increases with electrolysis time in the case of the former mechanism and is the same for the added particles in the case of the latter mechanism. The adsorption isotherm of the surfactant on the pigment particle surface shows that they form monolayers at saturation and their desorption starts at slightly above the critical micelle concentration (cmc). These results suggest that the films formed through the former and the latter mechanism are prepared by disruption of micelles and desorption of surfactant from the pigment surface, respectively.