Polypyrrole was electrochemically synthesized onto a gold electrode in the presence of sodium p-toluenesulfonate (TSNa) as the key dopant. Under the optimal synthesis condition, the surface morphology of PPy/TSNa was tailored and exhibited a nano-tentacle structure. The resulting rough and fuzzy morphology greatly enhanced the apparent surface area as well as the polymer film conductivity. Adenosine triphosphate (ATP) was then incorporated in the structure by subsequent ion exchanging. This procedure could be envisaged as pseudo-molecular templating to eliminate several shortcomings associated with physical templating. Fourier transform infrared (FTIR) and ultraviolet-visible (UV-vis) spectroscopy were conducted to investigate the incorporation of ATP. The pronounced rough surface of PPy/TSNa provided a higher density of active sites for ATP binding. The resulting PPy/ATP film exhibited a high charged capacity and lower impedance compared to the bare gold electrode. ATP remained stable in the PPy film; however, a negative bias to the electrode stimulated the conducting polymer to release ATP. This concept could serve as a mechanism for drug delivery and biosensing applications. (c) 2006 Wiley Periodicals, Inc. J Biomed Mater Res, 2006.