{We describe a method for characterizing self-assembled monolayers (SAMs) in terms of their performance as antirelaxation wall coatings for alkali atom vapor cells. A combination of initial surface analysis and subsequent laser spectroscopy is used to provide insight into the quality of the coating, as well as its performance under the exposure to alkalis as it occurs, for example, when used in applications such as atomic magnetometers or clocks. Fused silica plates coated with octadecyltrichlorosilane SAMs were used to make cubic Rb-87 gas cells. The surface was characterized by x-ray diffraction, contact angle measurements, and atomic force microscopy. Measurements of hyperfine resonance linewidths and frequency shifts show that the rubidium vapor atoms collide up to 40 times with the walls of the cells before their coherence relaxes and their adsorption energy is around 0.065 eV. Chemical analysis of the cell indicates some weak reactions between the coating and the rubidium atoms. (C) 2008 American Institute of Physics.}