In environmental catalysis the destruction or removal of nitrogen oxides (DeNOx process) is receiving a lot of attention. Synchrotron-based x-ray absorption near-edge spectroscopy, high-resolution photoemission, and first-principles density-functional calculations (DFT-GGA) were used to study the interaction of nitrogen dioxide with CeO2 and MgO. The only product of the reaction of NO2 with pure CeO2 at 300 K is adsorbed nitrate. The NO3 is a thermally stable species which mostly decomposes at temperatures between 450 and 600 K. For the adsorption of NO2 on partially reduced ceria (CeO2-x), there is full decomposition of the adsorbate and a mixture of N, NO, and NO3 coexists on the surface of the oxide at room temperature. Ce3+ cations can assist in the transformation of NO and NO2 in DeNOx operations. Adsorbed NO3 (main product) and NO2 are detected after exposing MgO to NO2 gas. A partial NO2,ads-->NO3,ads transformation is observed on MgO(100) from 150 to 300 K. DFT-GGA calculations show strong bonding interactions for NO2 on Mg sites of this surface, and dicoordination via O, O is more favorable energetically than monocoordination via N. The NO2,ads species disappears from magnesium oxide at temperatures below 600 K, whereas part of the NO3,ads is stable up to temperatures near 800 K. MgO can be very useful as a sorbent for trapping NO2. A general trend is found after comparing the chemical behavior of NO2 on different types of oxides (CeO2, MgO, TiO2, Fe2O3, CuO, ZnO). On all these systems, the main product after adsorbing NO2 at 300 K is nitrate with minor amounts of chemisorbed NO2 and no signs of full decomposition of the adsorbate. This trend and the results of DFT-GGA calculations indicate that NO2 is very efficient for the nitration (i.e., formation of NO3 as a ligand) of metal centers that are missing O neighbors in oxide surfaces.