The condensation kinetics of water and chloroform on Ag surfaces modified with ω-terminated alkanethiol self-assembled monolayers (SAMs) with -CH3, -OH, and -COOH terminal groups have been investigated using ellipsometry under conditions of different solvent vapor pressures up to saturated conditions. Condensed layers equilibrate rapidly with solvent vapor pressure as the pressure approaches saturation values after about 90-120 min of exposure to pure solvent in a closed cell. As expected, less solvent condenses at lower solvent vapor pressures for both solvents. Surprisingly, however, based on ellipsometrically-determined thicknesses, solvent condensation does not result in layers that exceed 0.4 nm for any system. For the system that exhibits the greatest spontaneous condensation of solvent, water on ω-carboxy-terminated SAMs, photoelastic modulation-infrared reflection absorption spectroscopy (PM-IRRAS) is used to verify the thickness measured with ellipsometry. Collectively, results suggest condensation of the first layer with relatively rapid kinetics. However, the absence of thicker condensed layers indicate that interactions between the first and subsequent layers of solvent are relatively weak, consistent with previous spectroscopic studies of thin solvent layers on SAMs from this laboratory.