Aluminas and their surface chemistry play a vital role in many areas of modern technology.The behavior of adsorbed water is particularly important and poorly understood. Simulations of hydrated [small alpha, Greek]-alumina (0001) surfaces with ab initio molecular dynamics elucidate many aspects of this problem, especially the complex dynamics of water dissociation and related surface reactions. At low water coverage, free energy profiles established that molecularly adsorbed water is metastable and dissociates readily, even in the absence of defects, by a kinetically preferred pathway. Observations at higher water coverage revealed rapid dissociation and unanticipated collective effects, including water-catalyzed dissociation and proton transfer reactions between adsorbed water and hydroxide. The results provide a consistent interpretation of the measured coverage dependence of water heats of adsorption, hydroxyl vibrational spectra, and other experiments.