Acacia tortuosa produces a clear gum, very soluble in water. Previous reports showed that it was constituted by four fractions, one of them an arabinogalactan–protein complex. The elucidation of the A. tortuosa gum structure by the combination of classical chemical methods, size exclusion chromatography and NMR spectroscopy, was the objective of this investigation. The data obtained show that the heteropolysaccharide is an arabinogalactan type II, highly ramified, with lateral chains at C-2 as well as at C-6 of the galactose 3-O residues; mono-O-substituted galactoses were not detected. There are residues of mannose, the arabinose, pyranose predominantly, is terminal and 2-O-linked. The abundance of the 4-O-methyl-a-D-glucuronic acid was no...