Amphiphilic (pyrrolylalkyl)ammonium monomers, differing in the size of their cationic polar headgroup -N+(CnH2n+1)3 (n = 1-4,6), have been synthesized and studied. Surfactant properties of these compounds have been examined. The monomer with n = 1 forms micelles in solution. All the other monomers do not lead to the formation of organized assemblies. However, they disperse in pure water upon sonication and lead to the formation of milky dispersions, from which monomer films are coated on an electrode surface and subsequently electropolymerized in an aqueous electrolyte. This process produces stable, electroactive cationic films which could incorporate bulky electroactive anions. The permeabilities and anion-exchange properties of these poly(amphiphilic pyrrole) films depend on the headgroup size of the monomer. Incorporation of electroactive anions could also be accomplished in one step, by electropolymerization of monomer-anion mixtures coated on an electrode surface. With the anthraquinonesulfonate anion, peak splitting of the cyclic voltammetry curve of the modified electrode studied in an aqueous electrolyte suggests a regular surface arrangement.