The structure of the crystalline addition product (1) formed between d-galactose and potassium bisulfite (potassium hydrogen sulfite) has been determined by X-ray diffraction analysis and compared with those structures reported for the related addition products from d-glucose and D-mannose. As with the latter two sulfonates, the D-galactose derived compound has an open-chain structure, with the carbon chain adopting a near planar zigzag conformation extending to the sulfur atom, similar to the d-mannose derivative but in contrast to the sickle conformation adopted by the d-glucose derivative. This last compound also differs in crystallising as a monohydrate. Inter-chain linking through cation coordination leads to a three dimensional network in the crystal.