Understanding the interaction of water with metal oxide surfaces is important to a diverse array of fields and is essential to the interpretation of surface charging and ion adsorption behavior. High-resolution specular X-ray reflectivity was used to determine the termination of and water adsorption on the alpha-Al2O3 (012)-aqueous solution interface. Interference features in the reflectivity data were used to identify the likely termination, consisting of a full Al2O3 layer plus an additional oxygen layer that completes the coordination shell of the upper aluminum site. This was further investigated through a model-independent inversion of the data using an error correction algorithm, which also revealed that there are two sites of adsorbed water above the surface. Characteristics of these two water sites were quantified through a model-dependent structural refinement, which also revealed additional layering in the interfacial water that gradually decays toward disordered bulk water away from the surface. Although the termination observed in this study differs from that assumed in past studies of surface charging, the density of key surface functional groups is unchanged, and thus, predictions of surface charging behavior are unchanged. As the pH(pzc) of this surface has yet to be modeled accurately, a full 3-dimensional surface structural analysis based on the termination observed in this study is needed so that the effects of surface functional group bond length changes on the pK(a) values can be incorporated. Consideration of the termination and sites of water adsorption suggest that singly coordinated oxygen groups will be the primary sites of ion adsorption on this surface.