Polythiophenes can be electrosynthesized by oxidative polymerization that would result in a polymer with a positively charged backbone that is compensated by the incorporation of counter-anions. Thus, the properties of the polymer can be designed by the judicious selection of substituents and/or the type of counter-anion incorporated. Polythiophenes can undergo electrochemical redox reactions. Tetrabutylammonium perchlorate was used as the electrolyte while the counter-anion, perchlorate, would be expelled from the polymer on reduction thus leaving the polymer backbone uncharged. The neutral polymer, behaved like a p-type semiconductor as both photoelectrochemical as well as Schottky devices were prepared.