By using small fluorinated ethers as models for perfluoropolyalkyl ether lubricants, we have been able to determine the effect of fluorine on the bonding and orientation of the alkylethers adsorbed on the Cu(111) surface. The desorption energies have been determined by using temperature-programmed desorption and the orientations by Fourier transform infrared absorption reflection spectroscopy (FT-IRAS). The model compounds studied were dioxolane (CH2OCH2OCH2) and perfluorodioxolane (CF2OCF2OCF2), diethyl ether ((CH3CH2)(2)O) and perfluorodiethyl ether((CF3CF2)(2)O), dimethoxymethane ((CH3O)(2)CH2) and perfluorodimethoxymethane ((CF3O)(2)CF2), dimethyl ether ((CH3)(2)O) and perfluorodimethyl ether ((CF3)(2)O). All of the molecules studied adsorb molecularly and reversibly on the Cu(lll) surface exhibiting first-order desorption kinetics. Upon fluorination of the alkyl ethers, the adsorbate-metal bond was weakened by 5-7 kcal/mol. The hydrogenated ethers exhibit repulsive adsorbate-adsorbate interactions, while the fluorinated ethers have attractive adsorbate-adsorbate interactions. At saturation coverages, the FT-IRAS spectra show that the diethyl ethers are oriented with their molecular axes parallel to the Cu(111) surface. 1,3-Dioxolane was oriented with its ring plane parallel to the metal surface.