Regiospecific substituted polyanilines have been assembled via electropolymerization of methoxy-substituted dimeric and trimeric oligoanilines. The oligoaniline monomers were synthesized utilizing Pd-catalyzed aryl amination cross-coupling chemistry. The single-crystal X-ray structure of one of the oligomers is presented. The oligoaniline monomers were electropolymerized in 1 M H2SO4, and the electrochemical behavior and potential-dependent in situ conductivities of the regiospecific polyaniline films were compared to those of random copolymers polymerized from solutions of aniline and o-anisidine of the same molar ratio. The regiospecific polyanilines exhibited higher conductivities, which may be attributed to a more crystalline and regular structure. Differences in the oxidation potential of the polymers are observed depending on the degree of methoxy substitution.