The self-aggregation properties of a pyrrole-substituted cationic surfactant have been studied using different techniques, including conductivity and surface tension measurements, potentiometry with a surfactant-selective electrode and cyclic voltammetry, Potentiometry gave good results for the determination of its critical micelle concentration (CMC) as well in pure water as in electrolytic media. Furthermore, in spite of the highly irreversible oxidation of the pyrrole group contained in the surfactant, cyclic voltammetry afforded a fast and valuable estimation of the CMC from peak current and peak potential variations.