The formation of self-assembled monolayers (SAMs) on gold from the adsorption of a series of specifically designed 2,2-dialkylpropanedithiol derivatives, [CH3(CH2)(n)](2)C[CH2SH](2) where n = 0, 3, 7, and 11-15, is reported. The SAMs were characterized by optical ellipsometry, contact angle goniometry, and polarization modulation infrared reflection absorption spectroscopy. These data, when compared to those collected on SAMs generated from normal alkanethiols (CH3(CH2)(m)SH) of similar chain length, suggest that the new SAMs are highly oriented and well packed. They exhibit, however, slightly less crystallinity than their alkanethiolate-based analogues. A preliminary description of the kinetics of adsorption and desorption of these new SAMs is presented.