Electrochemical properties of well-defined molecular structured polyamide with amine-capped aniline pentamer in the main chain and conventional polyaniline were investigated and discussed. CV results suggest that the synthesized polyamide shows a relatively complicated redox process than conventional polyaniline during potential cycling. Differences in ESI characterization revealed that the synthesized polyamide exhibits higher electronic conductivity and lower resistance than the conventional polyaniline. The analysis of molecular configuration based upon the quantum chemistry calculation reveal that the difference in electrochemical activity and conductivity should be ascribed to the influence of system energy, skeleton conjugation, and the Fermi energy of the bipolaron model in the polymer molecules. (c) 2007 Wiley Periodicals, Inc.