Perfluorinated organic film C8F17-4-C6H4- was successfully grafted on in situ reduced gold by reductive grafting from the diazonium tetrachloroaurate (III) salt [C8F17-4-C6H4N N]AuC14. The highly irreversible broad reduction peak of 1.0 mM [C8F17-4-C6H4N N]AuC14 occurs at - 0.08 V vs. Ag/AgCl in 0.1 M [BU4N]PF6/CH3CN at a glassy carbon working electrode. The surface morphology and evidence of the gold-organic film formation was investigated by attenuated total reflectance-infrared spectroscopy (ATR-IR), optical microscopy (OM), scanning electron microscopy (SEM), energy dispersive X-ray spectroscopy (EDS), and atomic force microscopy (AFM). ATR-IR spectrum shows the v(c-F) stretching frequencies of the perfluorinated film at 1089 and 1230 cm(-1) and the absence of the diazonium peak at 2305 cm(-1). OM, SEM, and AFM images show clusters or islands and isolated sub-micron deposits protruding less than one micron above the surface. EDS measurements showed the presence of gold in the thin film. Ferrocene/ferrocenium and [Fe(CN)(6)](3-/4-) electron-transfer experiments, sonication in organic solvents and water, and open circuit potential (OCP) experiments showed the efficient grafting and robustness of the grafted film. Published by Elsevier B.V.