New larger-scale (10 g monomer in 500 cm(3)) methods for the electropolymerization of alkylpyrroles in quantity have been developed. These methods offer the advantage of electropolymerization with fractionation in a single step. Galvanostatic, potentiostatic and potentiodynamic methods have been considered. 3-Octadecylpyrrole was electrochemically synthesized in dichloromethane. The use of other solvent systems, namely dichloromethane/acetonitrile, carbon tetrachloride/dichloromethane or tetrahydrofuran/acetonitrile mixtures, has also been considered. Furthermore, the new copolymer of 3-octadecylpyrrole with pyrrole was successfully grown in dichloromethane/acetonitrile medium. The investigations were extended to 5-octylpyrrole, which was successfully electropolymerized. The products are conductive, some are electroactive and many can be dissolved in common organic media. The solubilities (some in excess of 50% by weight) of these polymers and their conductivities (as high as 31.4S cm(-1)) are reported. The yields and conductivities are dependent upon the solvent system and electrolyte used for electrosynthesis. The solvent system used for electrosynthesis also affected the solubility of the polymers produced. For cast films, the electroactivity depended not only upon the polymer but also upon the casting solvent.