The rational design, synthesis, and characterization of a series of novel perfluorinated dendrons 14a,b, 25a,b, 26a,b, and 18 are described. The dendrimers were designed to have a thiol at the focal point for attachment to a gold surface to enable the fabrication of self-assembled monolayers (SAMs). Perfluorinated tails were attached to the periphery to provide solubility in supercritical carbon dioxide, and to increase the hydrophobicity and the stability of self-assembled monolayers formed. Mitsunobu reactions were utilized to provide high-yielding steps allowing large-scale production of the novel dendrimers.