Micellar and interfacial behavior of electropolymerizable cationic surfactants containing a pyrrole group, and associated with various counteranions (bromide, nitrate, tetrafluoroborate and tosylate), have been investigated in pure water and in aqueous electrolytes. Results have been compared to that for the regular dodecyltrimethylammonium surfactant. The influence on the micellization process of counteranion binding, cationic headgroup size, and position of the pyrrole moiety (at the end of the lipid tail or close to the headgroup) has been studied in detail. H-1 NMR experiments carried out in nonmicellar and in micellar solutions have shown that the pyrrole group remained confined in the micelle core.