Sulfur K-edge X-ray absorption near-edge structure (XANES) spectra have been recorded and the S(1s) electron excitations evaluated by means of density functional theory-transition potential (DFT-TP) calculations to provide insight into the coordination, bonding, and electronic structure. The XANES spectra for the various species in sulfur dioxide and aqueous sodium sulfite solutions show considerable differences at different pH values in the environmentally important sulfite(IV) system. In strongly acidic (pH < similar to 1) aqueous sulfite solution the XANES spectra confirm that the hydrated sulfur dioxide molecule, SO2(aq), dominates. The theoretical spectra are consistent with an OSO angle of similar to 119 degrees in gas phase and acetonitrile solution, while in aqueous solution hydrogen bonding reduces the angle to similar to 116 degrees. The hydration affects the XANES spectra also for the sulfite ion, SO32-. At intermediate pH (similar to 4) the two coordination isomers, the sulfonate (HSO3-) and hydrogen sulfite (SO3H-) ions with the hydrogen atom coordinated to sulfur and oxygen, respectively, could be distinguished with the ratio HSO3-:SO3H- about 0.28:0.72 at 298 K. The relative amount of HSO3 increased with increasing temperature in the investigated range from 275 to 343 K. XANES spectra of sulfonate, methanesulfonate, trichloromethanesulfonate, and trif I uorom ethanesulfonate compounds, all with closely similar S-O bond distances in tetrahedral configuration around the sulfur atom, were interpreted by DFT-TP computations. The energy of their main electronic transition from the sulfur K-shell is about 2478 eV. The additional absorption features are similar when a hydrogen atom or an electron-donating methyl group is bonded to the -SO3 group. Significant changes occur for the electronegative trichloromethyl (Cl3C-) and trifluoromethyl F3C-) groups, which strongly affect the distribution especially of the 7 electrons around the sulfur atom. The S-D bond distance 1.38(2) angstrom was obtained for the deuterated suffonate (DSO3-) ion by Rietveld analysis of neutron powder diffraction data of CsDSO3. Raman and infrared absorption spectra of the CsHSO3, CsDSO3, H3CSO3Na, and Cl3CSO3Na-H2O compounds and Raman spectra of the sulfite solutions have been interpreted by normal coordinate calculations. The C-S stretching force constant for the trichloromethanesulfonate ion obtains an anomalously low value due to steric repulsion between the Cl3C- and -SO3 groups. The S-O stretching force constants were correlated with corresponding S-O bond distances for several oxosulfur species.