Self-assembled monolayers of terminally fluorinated alkanethiols, CF3(CH2)(n)SH with n = 9-15, and their nonfluorinated analogues, CH3(CH2)(n)SH with n = 9-15, were prepared by adsorption from solution onto evaporated gold. The monolayers were characterized by contact angle goniometry, ellipsometry, and X-ray photoelectron spectroscopy. The analyses indicate that the CF3-terminated alkanethiols generate terminally fluorinated monolayers that are well-ordered, particularly when the chain lengths consist of 12 or more carbon atoms. Comparison of CF3-terminated films to CH3-terminated films of similar length reveals that terminal fluorination of the surface leads to an overall decrease in the surface tension of the films. This decrease arises from a relatively large decrease in the dispersive component of the surface tension upon the introduction of fluorine. Surprisingly, terminal fluorination also leads to a small but significant increase in the nondispersive component(s) of the surface tension. The origin of these opposing effects is discussed.