Radical forms of sulfur dioxide (SO2), sulfite (SO32−), sulfate (SO42−), and their conjugate acids are known to be generated in vivo through various chemical and biochemical pathways. Oxides of sulfur are environmentally pervasive compounds and are associated with a number of health problems. There is growing evidence that their toxicity may be mediated by their radical forms. Electron paramagnetic resonance (EPR) spin trapping using the commonly used spin trap, 5,5-dimethyl-1-pyrroline N-oxide (DMPO), has been employed in the detection of SO3•− and SO4•−. The thermochemistries of SO2•−, SO3•−, SO4•−, and their respective conjugate acids addition to DMPO were predicted using density functional theory (DFT) at the PCM/B3LYP/6-31+G**//B3LYP/6-31G* level. No spin adduct was observed for SO2•− by EPR but an S-centered adduct was observed for SO3•− and an O-centered adduct for SO4•−. Determination of adducts as S- or O-centered was made via comparison based on qualitative trends of experimental hfcc’s with theoretically calculated ones. The thermodynamics of the non-radical addition of SO32− and HSO3− to DMPO followed by conversion to the corresponding radical adduct via the Forrester-Hepburn mechanism was also calculated. Adduct acidities and decomposition pathways were investigated as well, including an EPR experiment using H217O to determine the site of hydrolysis of O-centered adducts. The mode of radical addition to DMPO is predicted to be governed by several factors, including spin population density, and geometries stabilized by hydrogen bonds. The thermodynamic data supports evidence for the radical addition pathway over the nucleophilic addition mechanism.