CeO2 and Cu/CeO2 are effective catalysts/sorbents for the removal or destruction of SO2. Synchrotron-based high-resolution photoemission, X-ray absorption near-edge spectroscopy (XANES), and temperature-programmed desorption (TPD) have been employed to study the reaction of SO2 with pure and reduced CeO2 powders, ceria films (CeO2, CeO2-x, Ce2O3+x) and model Cu/CeO2 catalysts. The results of XANES and photoemission provide evidence that SO4 was formed upon the adsorption of SO2 on pure powders or films of CeO2 at 300 K. The sulfate decomposed in the 390-670 K temperature range with mainly SO2 and some SO3 evolving into gas phase. At 670 K, there was still a significant amount of SO4 present on the CeO2 substrates. The introduction of O vacancies in the CeO2 powders or films favored the formation of SO3 instead of SO4. Ceria was able to fully dissociate SO2 to atomic S only if Ce atoms with a low oxidation state were available in the system. When Cu atoms were added to CeO2 new active sites for the destruction of SO2 were created improving the catalytic activity of the system. The surface chemistry of SO2 on the Cu-promoted CeO2 was much richer than on pure CeO2. The behavior of ceria in several catalytic processes (oxidation of SO2 by O-2, reduction of SO2 by CO, automobile exhaust converters) is discussed in light of these results.