The interaction of cesium at the (0001) and (1102) surfaces of sapphire has been investigated using a variety of surface analytical techniques. Reflection mass spectrometric measurements yield initial Cs adsorption probabilities of 0.9 and 0.85 for the unreconstructed (0001) and (1102) surfaces, respectively. The adsorption probability decreases dramatically for these surfaces at critical Cs coverages of 2.0×10 14 and 3.4×1014 atoms/cm2, respectively. Thermally induced reconstruction of the (0001) surface to form an oxygen deficient surface results in a decrease in the initial probability and capacity for Cs adsorption. Low energy electron diffraction (LEED) demonstrates that an intermediate, mixed domain surface yields an initial adsorption probability of 0.5 while a reconstructed surface yields a value of 0.27. Thermal desorption mass spectrometry (TDMS) shows that surface reconstruction eliminates the high binding energy states of Cs (2.7 eV/atom), consistent with the observed changes in adsorption probability. In contrast, reconstruction of the (1102) surface produces only minor changes in Cs adsorption. Xray photoelectron spectroscopy (XPS) indicates that no formal reductive/oxidative chemistry takes place at the interface. We interpret the facile adsorption and strong binding of Cs on sapphire to result from Cs interacting with coordinatively unsaturated oxygen.