By using multinuclear (1H, 13C, 17O, 95Mo, 183W) magnetic resonance spectroscopy (1D and 2D), D-gulonic acid is found to form ten and seven complexes, respectively, with tungsten(VI) and molybdenum(VI), in aqueous solution, depending on pH and metal-ligand molar ratios. Two isomeric 1:2 (metal-ligand) complexes involving the carboxylate and the adjacent OH group are present in the pH range 2-9. At intermediate and high pH, molybdate forms a 2:1 tetradentate complex involving the four secondary hydroxyl groups, whereas tungstate forms one 2:1 terdentate species. At low and intermediate pH values, three 2:1 complexes are found for both metals, involving the carboxylate group and three secondary hydroxyl groups, as well as a 5:2 species involving the carboxylate group and all the secondary hydroxyl groups; the concentration of this species increases in time mainly at the expense of 2:1 and 1:2 complexes. Tungstate can also form two additional species, probably a 5:2 species involving the carboxylate group and all the hydroxyl groups, and a 2:1 pentadentate species involving the carboxylate group and all the secondary hydroxyl groups. In alkaline solutions, tungstate is able to form an additional 2:1 pentadentate complex involving all the hydroxyl groups.