The adsorption onto glassy carbon electrodes and the electrochemical oxidation in aqueous sodium tosylate or potassium nitrate electrolyte of micelle-forming cationic surfactants derived from pyrrole is described. Electrode coating by nonelectroactive, thin anion-exchanger films was observed, along with the formation of degradation products following reaction between oxidized pyrrole and water. The best film deposition efficiency was obtained with the more hydrophobic pyrrole-surfactant, which is characterized by the lower critical micelle concentration. The formation of conducting polymer films was successfully achieved by electro-oxidation of adsorbed layers of surfactant in electrolytes containing tetrafluoroborate or perchlorate anions, which decrease the solubility of the surfactant in water, thus increasing the hydrophobic character of the monomer layer.