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]AuCl4. The highly irreversible broad reduction peak of 1.0mM [C8F17-4-C6H4N≡N]AuCl4 occurs at −0.08V vs. Ag/AgCl in 0.1M [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 νC-F stretching frequencies of the perfluorinated film at 1089 and 1230cm−1 and the absence of the diazonium peak at 2305cm−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.