The gas‐phase geometries, dipole moments, enthalpies, and Gibbs free energies of dithionic acid H2S2O6, trithionic acid H2S3O6, tetrathionic acid H2S4O6, and disulfuric acid H2S2O7 have been determined by ab initio MO calculations at various levels of theory. The most stable conformations of H2S2O6 and H2S2O7 are of C2 symmetry, the other two acids are of C1 symmetry. The gas‐phase acidities defined as ΔG°298 of the deprotonation reaction obtained at the {MP2/6‐311++ G(3df, 3pd)//MP2/6‐31+ G(d) + ZPVE[HF/6‐31+ G(d)]} level are as follows [kJ·mol−1]: H2S2O6 1180, H2S3O6 1162, H2S4O6 1156, H2S2O7 1171. All four acids are much stronger than fluorosulfuric acid and chlorosulfuric acid in the gas phase. The decomposition of H2S2O7 into SO3 and H2SO4 is slightly endothermic and the same holds for the decomposition of H2S3O6 into SO3 and H2S2O3, but the reaction of H2S2O6 to SO2 and H2SO4 is strongly exothermic. The structures of the monoanions HS2O6−, HS3O6−, HS4O6−, and HS2O7− are characterized by intramolecular hydrogen bonds.