Thin layers with interesting electronic materials application can be synthesized via the adsorption of discrete organometallic complexes on appropriately activated metal, semiconductor, and insulator surfaces. The extent of hydroxylation of these surfaces can affect both the coverage and reaction chemistry for the adsorption of organometallics, and provides a convenient, controlable route to the formation of a number of thin film materials. Ambient condition and ultrahigh vacuum methods have been used to characterize these interactions and to develop synthetic strategies for the covalent attachment of organometallic species that can stabilize organic monolayers on these surfaces.