This photoelectron spectroscopy (PES) study compares the adsorption and subsequent decomposition of methanol on a Pd(111) single crystal and Pd particles on a CeO2(111)/Cu(111) thin film surface investigated by means of XPS and soft X-ray synchrotron-radiation-excited PES. Resonance PES (Ce 4d -> 4f transitions) was used to determine the Pd deposit and cerium oxide surface interaction with high sensitivity. Methanol adsorbed at low temperature formed adsorbate multilayers, which were consecutively desorbed upon stepwise annealing to 600 K. The results obtained on Pd/CeO2(111) showed a more complex decomposition process involving different possible pathways compared to the single pathway decomposition to CO on the Pd(111) surface. [GRAPHICS] .