Conducting polymer monolayers of poly(3-octylthiophene) (POT) on gold electrodes were prepared by a self-assembly technique. Infrared spectroscopic, ellipsometric and contact angle goniometric measurements indicate a highly organized and densely packed supermolecular structure on the gold surface. Upon chemical doping in an aqueous solution, the monolayer shows a dramatic change in voltammetric responses towards the redox probe in the solution. The self-assembled conducting polymer films exhibit better thermal stability in wet environments, suggesting that multi-anchoring effects of the polymer improve the integrated adhesion and the binding stability of the self-assembled POT monolayers. The monolayers were also characterized by electrochemical techniques.