The preparation and functionalization of ITO surfaces has been studied using primarily X-ray photoemission spectroscopy and infrared reflection-absorption spectroscopy (IRRAS) and the reagents n-hexylamine and n-octyltrimethoxysilane ( OTMS). Particular attention has been paid to characterization of the surfaces both before and after functionalization. Surfaces cleaned by ultraviolet (UV)/ozone treatment and subsequently exposed to room air have similar to 0.5-0.8 monolayers (ML) of adsorbed impurity C. Most is in the form of aliphatic species, but as much as one-half is partially oxidized and consists of C-OH, C-O-C, and/or > C=O groups. The coverage of these species can be reduced by cleaning in organic solvents prior to UV/ozone treatment. The OH coverage on the ITO surfaces studied here is relatively small (similar to 1.0 OH nm(-2)), based on the Si coverage after reaction with OTMS. A satellite feature in the O 1s XPS spectrum, often suggested to be a quantitative measure of adsorbed OH, receives a significant contribution from sources not directly related to hydroxylated ITO. n-Hexylamine adsorbs, at a saturation coverage of similar to 0.08 ML, via a Lewis acid-base interaction. The particular acid site has not been conclusively identified, but it is speculated that surface Sn sites may be involved. For OTMS, a saturation coverage of about 0.21 ML is found, and the C/Si atom ratios suggest that some displacement of preadsorbed organic impurities occurs during adsorption. The alkyl chain of adsorbed OTMS is disordered, with no preferred stereoisomer. However, the chain appears to lie mainly parallel to the surface with the plane defined by the terminal CH3-CH2-CH2- segment oriented essentially perpendicular to the surface.