It was found that plasmid DNA can act as an attractive template for oxidative polymerization of pyrrole and result in the novel higher-order superstructures composed of the conductive polymers. The TEM and SEM observation estabilished that poly(pyrrole) grows up to nanosized rod-like, circular, and Supercoiled structures reflecting the higher-order conformation of plasmid DNA. The obtained polymer structures are drastically changed reflecting the controlled DNA morphologies used as their templates.