Electroreduction of aryl diazonium salts on gold can produce organic films that are more robust than their analogous self assembled monolayers formed from chemical adsorption of organic thiols on gold. However, whether the enhanced stability is due to the Au-C bond formation remains debated. In this work, we report the electroreduction of an aryl diazonium salt of 4,4'-disulfanediyldibenzenediazonium on gold forming a multilayer of Au-(Ar-S-S-Ar), which can be further degraded to a monolayer of Au-Ar-S- by electrochemical cleavage of the S S moieties within the multilayer. By conducting an in situ surface -enhanced Raman spectroscopic study of both the multilayer formation/degradation and the monolayer reduction/oxidation processes, coupled to density functional theory calculations, we provide compelling evidence that an Au C bond does form upon electroreduction of aryl diazonium salts on gold and that the enhanced stability of the electrografted organic films is due to the Au C bond being intrinsically stronger than the Au S bond for a given phenylthiolate compound by ca. 0.4 eV.