A model for the surface structure of rutile is proposed, based on infra-red studies of a crystalline rutile sample prepared by the combustion of Ti(iso-PrO)4. It is suggested that the exterior surfaces of the rutile crystals correspond to three low index crystal planes—namely the (100), (101) and (110). Of these the first two are capable of adsorbing molecular water as ligand coordinated to Ti4+ surface ions, whereas the (110) crystal face adsorbs water dissociatively leading to the presence of equal quantities of two types of OH– ions. One of these types is associated with a surface Ti4+ ion which is five coordinate with respect to lattice oxide ions whereas the other type is bound to a surface Ti4+ ion which is only four fold oxide ion coordinate. It is possible to rationalize the observed thermal dehydroxylation and dehydration properties of the oxide and also account for its pyridine adsorption properties.