The self-assembly process of monolayers has been exploited as a tool to order and orient molecules with particular functions on flat gold surfaces in two dimensions. These functional adsorbates were derivatized with sulfide moieties for the adsorption on gold. The studied adsorbates include resorcin[4]arenes, calix[4]arenes, and carceplexes. Monolayers of these adsorbates on gold were prepared and characterized by means of a combination of various surface analytical techniques, including infrared spectroscopy, wetting, ellipsometry, X-ray Photoelectron Spectroscopy (XPS), Secondary Ion Mass Spectrometry (SIMS), electrochemistry, and Atomic Force Microscopy (AFM). The monomolecular films were studied for potential applications like sensing and switching.