Methylation and 13C NMR analyses were carried out on the high-arabinose, acidic heteropolysaccharide of gum ghatti and the products obtained on three successive, controlled Smith degradations. The side chains contained mainly 2-O- and 3-O-substituted Araf units. Of these the second degradation eliminated remaining alpha-Araf units, and their beta anomers became evident. The proportion of Galp units gradually increased in the form of nonreducing end- and Galp units, although 3,6-di-O- and 3,4,6-tri-O-substituted Galp units diminished. After three degradations groups with consecutive 3-O-substituted beta-Galp units were formed. The proportion of periodate-resistant 3-O- and 2,3-di-O-substituted Manp units was maintained. As a guide to side-chain structures in the polysaccharide, seven of the 10 free reducing oligosaccharide fractions (PC) present in the gum were isolated and examined (NMR, ESIMS, and sometimes methylation analysis). Characterized are alpha-Araf-(1 --> 2)-Ara and three Ara-containing oligosaccharide fractions containing 2-O- and 3-O-substituted units. These gave respectively, ESIMS molecular ions arising from Ara(2), beta-Araf oligosaccharides with four units, beta-Araf oligosaccharides with seven units, and Hex(2)-Ara(4). Alpha-Rhap-(1 --> 4)-GlcA, alpha-Rhap-(1 --> 4)-beta-GlcpA-(1 --> 6)-Gal, and alpha-Rhap-(1 --> 4)-beta-GlcpA-(1 --> 6)-beta-Galp-(1 --> 6)-Gal represented other side chains.