Density functional molecular cluster calculations have been used to investigate the interaction of SO(2) with defect-free TiO(2)(110) and Ti(2)O(3)(102) surfaces. Adsorbate geometries and chemisorption enthalpies have been computed and discussed. Several local minima have been found for TiO(2)(110), but only one seems to be relevant for the catalytic conversion of SO(2) to S. In agreement with experiment, the bonding of SO(2) to Ti(2)O(3)(102) is much stronger than that on TiO(2)(110). Moreover, our results are consistent with the surface oxidation and the formation of strong Ti-O and Ti-S bonds. On both substrates, the bonding is characterized by a two-way electron flow involving a donation from the SO(2) HOMO into virtual orbitals of surface Lewis acid sites (), assisted by a back-donation from surface states into the SO(2) LUMO. However, the localization of surface states and the strength of back-donation are very different on the two surfaces. On TiO(2)(110), back-donation is weaker, and it involves unsaturated bridging O atoms, while on Ti(2)O(3)(102), it implies the -based valence band maximum and significantly weakens the S-O bond.