The tridentate adsorbates cyclohexane-cis,cis-1,3,5-triyltrimethanethiol (CyTSH) and (cis,cis-1,3,5-trimethylcyclohexane-1,3,5-triyl)trimethanethiol (3C1CyTSH) were designed and synthesized. Thin films prepared by the adsorption of these molecules onto the surface of gold were characterized by ellipsometry, contact angle goniometry, polarization modulation infrared reflection absorption spectroscopy, and X-ray photoelectron spectroscopy (XPS). CyTSH was found to generate multilayer thin films with many unbound thiol species and oxidized sulfur moieties (e.g., disulfides and sulfones). In contrast, 3C1CyTSH was found to generate monolayer films in which similar to 90% of the thiols were bound to the surface of gold (similar to 10% unbound), and there were no oxidized sulfur species. In comparing CyTSH and 3C1CyTSH, the methyl groups of 3C1CyTSH impart rigidity to the structure, which significantly enhances the chemisorption of sulfur to the surface of gold. Ellipsometric measurements and analysis by XPS indicate that the thickness of the self-assembled monolayer formed from 3C1CyTSH is similar to 5 angstrom.