The copolymerization of pyrrole (Py) with N-ethyl pyrrole, N-butyl pyrrole, and N-octyl pyrrole (NOPy) was carried out by electrochemical and chemical oxidation. In the electrochemical method, copolymer thin films with different feed ratios of monomers were synthesized by the cyclic voltammetry method in a lithium perchlorate (LiClO4)/acetonitrile (CH3CN) electrolyte on the surface of a glassy carbon working electrode. The deposition conditions on the glassy carbon, the influence of the molar ratios of the monomers on the formation of the copolymers, and the electroactivity of the copolymers were investigated with cyclic voltammetry. Nanoparticles made of a conjugate of the copolymers with different feed ratios of monomers were prepared by chemical polymerization (conventional and interfacial methods) in the presence of iron(III) chloride hexahydrate (FeCl3 center dot 6H2O) as the oxidant. Nanostructural copolymers with higher conductivities were synthesized by simple tuning of the preparation conditions in a two-phase medium. Fourier transform infrared spectroscopy, scanning electron microscopy, and four-probe conductivity measurement techniques were applied for the characterization of the obtained copolymers. The conductivity of the obtained copolymer by an interfacial method with chloroform as the organic phase was 20 times higher than the copolymer obtained via an interfacial method with toluene as the organic phase and 700 times higher than the copolymer prepared by the conventional method (for a molar ratio of 70 : 30 Py : NOPy). (C) 2011 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem, 2012