The adsorption structure of phenylphosphonic acid (PPOA) on an alumina surface was investigated as a function of exposure and temperature using infrared reflected absorption spectroscopy (IRAS) and a Kelvin probe. The alumina surface was held at room temperature during deposition. At monolayer adsorption, P-O and PhenyI-P bands are observed, which indicate the creation of P-O-Al bonds. The aromatic ring plane is positioned perpendicular to the surface, i.e. deprotonated PPOA stands vertically on the surface. At multilayer adsorption, P=O and P-OH bands appear in the spectra. The multilayer PPOA film starts to desorb at 400 K. From 400 to 700 K, the IRAS spectra are similar to the monolayer spectrum, indicating that the multilayer structure reverses to the monolayer-like PPOA adlayer by heating. The acid molecules start to desorb at 700 K. Crown Copyright (C) 2009 Published by Elsevier B. V. All rights reserved.