In the study described here, the surface structure of a self-assembly octyl hydroxamic acid at a calcium fluoride (CaF2) surface is evaluated using sum-frequency vibrational spectroscopy (SFVS). Of particular significance are the results that show octyl hydroxamic acid adsorbs at the fluorite surface from octanol solution and has more ordering and molecular conformation than the octyl hydroxamic acid adsorbed from solution. At the fluorite/0.1 M octyl hydroxamic acid octanol solution interface a bilayer-like structure consisting of an octyl hydroxamic acid layer in contact with fluorite and a tilted alcohol layer was observed by SFVS. The alcohol molecules are oriented with respect to the hydroxamic acid monolayer with the OH groups directed towards the bulk alcohol phase and the terminal CH3 group oriented to face the alkyl chains of the hydroxamic acid monolaver. (c) 2008 Elsevier Inc. All rights reserved.