Abstract Zirconium hydroxide (Zr(OH) 4) is a catalytic support material whose reactivity depends on intrinsic surface hydroxyl groups. Here we present a 1H MAS NMR study where we identify bridging and terminal hydroxyl groups along with their concentrations even in completely dehydrated material. The dehydrated material contains 13 mmol/g bridging hydroxyl groups and 3.9 mmol/g terminal hydroxyl groups, yielding a ratio of 3.4:1, and is verified by XPS. Upon hydration, the number of surface hydroxyl groups remains constant while only bulk water is adsorbed on the surface. Knowing both the types and amounts of surface hydroxyl groups on Zr(OH) 4 helps explain the catalytic activity of Zr(OH) 4 in many applications.