The adsorption of sulfur dioxide (SO 2 ) on polycrystalline Cr2O3 was experimentally investigated using temperature-programmed desorption (TPD). The chemisorption of SO 2 on the (0001) surface was also studied using theoretical methods. Different adsorption geometries were explored for SO 2 adsorption on the α-Cr2O3 (0001) surface. Two similar adsorption configurations were found to be the most stable with chemisorption energies of −3.09 and −2.79eV/molecule. In both calculated stable adsorption configurations the appearance of sulfite-like species is predicted on the (0001) surface after adsorption. It is important to emphasize that these results are predicted only within the DFT+U framework. Under these conditions and despite great efforts, no stable sulfate-like geometry was found on this surface. The TPD spectrum exhibit a desorption peak at T p ≈870°C with a heating rate of β≈0.12°C/s. The desorption energy calculated by the analysis given by Redhead and Adams, assuming the rate of desorption is given by a Polanyi–Wigner equation, is ≈ −3.12eV. This value is in good agreement with the predicted one using DFT+U calculations. To our knowledge, this is the first theoretical study of SO 2 adsorption on the Cr2O3 (0001) surface.