A novel method is described for the determination of sequential side-chain structures in the complex, high-arabinose polysaccharide of the gum exudate of angico branco (Anadenanthera colubrina), using as basis the structurally similar reducing oligosaccharides present in small quantities. Of the ten detected, eight were characterized as disaccharides (2, 3, and 9), linear trisaccharides (1 and 4), branched pentasaccharides (5 and 6), and a doubly branched heptasaccharide (8). The oligosaccharides are substituents of the polysaccharide, which has a (1-->3)-linked beta-D-galactopyranosyl main chain, and with two exceptions they had 6-O-substituted galactopyranosyl reducing ends, probably corresponding to its main-chain units. Characterization was effected through their 1D and 2D NMR correlation spectra, which were better resolved and more readily interpretable than those of the polysaccharide. These spectral data were supported by monosaccharide composition and rotation values. Controlled Smith degradations and methylation analyses were carried out when it was necessary. These data were confirmed by field-desorption MS.