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The title salt, Na+·C6H13O9S−·H2O, crystallizes with three independent cations, molecular anions and solvent water molecules in the asymmetric unit. This crystalline monohydrate addition product, formed by reaction of d-glucose and sodium hydrogen sulfite in water, forms a three-dimensional network through complex cation coordination and extensive intermolecular hydrogen bonding. Each of the independent molecules has an open-chain structure with the carbon chains adopting a sickle-like conformation, similar to that found in the potassium salt [Cole et al. (2001). Carbohydr. Res. 335, 1–10], but there are significant differences in the patterns of complexation.