Self-assembled monolayers (SAMs) were generated by the adsorption of tert-butyl-terminated alkanethiols having the general formula (CH3)3C (CH2)nSH (n = 12-15) on the surface of gold. These monolayers were characterized by optical ellipsometry, contact angle goniometry, x-ray photoelectron spectroscopy, and polarization modulation infrared reflection absorption spectroscopy. The frictional properties of these new SAMs were compared to the analogous methyl-, isopropyl-, and trifluoromethyl-terminated SAMs.