Aqueous solutions containing pyrrole and calix-6-arenehexasulfonic acid were found to undergo polymerization in the absence of either a chemical oxidant or electrochemical oxidation. The product was an unstable colloidal suspension consisting of spherical polypyrrole particles measuring ≥500 nm in diameter. Conductivity measurements showed the material to be insulating, while cyclic voltammetry studies demonstrated that it was electroactive. Infrared spectroscopy and microanalysis confirmed that the polypyrrole produced was doped with calix-6-arenehexasulfonic acid. When the reaction was repeated using solutions containing stabilizing agents, stable colloidal dispersions were obtained. These were shown by both particle size analysis and transmission electron microscopy to contain much smaller particles than the unstabilized material, while cyclic voltammetry studies again demonstrated that the polypyrrole obtained was electroactive and sensitive to changes in the surrounding electrolyte.