The in situ formation of prototypes of complex hybrid organic structures gives the opportunity to characterize their morphologic and spectroscopic properties, a mandatory step toward the development of more reliable and efficient organic devices. In this context, a proper functionalization of the substrate’s surface is required for the linkage of small molecules or proteins. We report here how thin films of cysteamine have been successfully assembled on Au(111) by evaporation in ultra high vacuum conditions. The molecular orientation has been investigated by means of X-ray absorption spectroscopy. Both monolayer and multilayered films of cysteamine have been characterized by means of high-resolution photoemission spectroscopy. A compact, homogeneous self-assembled monolayer has been obtained, which provides the functionalization of the surface with a −NH2 linker. The investigation on the multilayer film revealed the presence of a zwitterionic cysteamine moiety.