Methanol adsorption and reaction have been studied on Rh-deposited cerium oxide thin films under UHV conditions using temperature-programmed desorption and synchrotron soft X-ray photoelectron spectroscopy. The methanol behavior was examined as a function of the Ce oxidation state, methanol exposure, and Rh particle size and coverage. When Rh nanoparticles were deposited on the ceria films, methanol decomposed on Rh to CO and H below 200 K. H atoms recombined and desorbed between 200 and 300 K. CO evolved from Rh deposited on fully oxidized ceria between 400 and 500 K. However, on reduced ceria films, the CO on Rh further decomposed to atomic C. Methanol adsorbed on the ceria films deprotonated to form methoxy as the only intermediate on the surface. This methoxy decomposed and desorbed as CO and H-2 at higher temperatures regardless of the ceria oxidation state. Compared with the methanol reaction on Rh-free ceria thin films, formaldehyde formation from methoxy was completely suppressed after Rh deposition. Our results indicate that Rh can promote the decomposition of methoxy adsorbed on the ceria and that decomposition of methoxy intermediates occurred at the metal/oxide interfaces. On the other hand, the reduced ceria can promote total methanol decomposition on Rh.