The synthesis of various omega-(N-pyrrolyl)alkanethiols and electrochemical characterization of the resulting monolayers on Au is described. Cyclic voltammograms of the monolayers on Au in Bu(4)NClO(4)/CH3CN display an irreversible wave at +1.00 V vs SSCE due to oxidation of pyrrole sites in the monolayer. There is no voltammetric evidence for polymerization of the surface-confined pyrrole units when the potential is scanned between 0 and +1.3 V in Bu(4)NClO(4)/CH3CN. Poly(pyrrole) films deposited on omega-(N-pyrrolyl)alkanethiol/Au surfaces are extremely adherent and smooth. Scanning electron micrographs of the polymers show that the films are composed of nuclei 80-100 nm in diameter. The differences between poly(pyrrole) formed on modified and unmodified Au are discussed.