The polysaccharide isolated from the gum exudate of palm Scheelea phalerata (SPN) was water-insoluble and composed of Fuc, Ara, Xyl, and uronic acid moieties in a 5:34:54:7 molar ratio: 12% of phenolics were also present. A soluble polysaccharide (SPNa) was obtained after alkaline treatment, which contained Fuc, Ara, Xyl and uronic acid in a 7:44:42:7 molar ratio, with only 2% phenolics. SPNa had an M w∼1.04×10 5 g mol −1 and was almost monodisperse ( M w/ M n:1.25±0.22). It had a branched structure with side chains of 2- O-substituted Xyl p (∼8%) and 3- O-substituted Ara f (12%) units, and a large proportion of nonreducing end-units of Ara f (15%), Fuc p (10%), Xyl p (4%), and Ara p (6%). The (1 → 4)-linked β-Xyl p main-chain units were 3- O- (9%), 2- O- (13%), and 2,3-di- O- (13%) substituted. Its 13C NMR spectrum contained at least 9 C-1 signals, those at δ 108.6 and 107.7 arising from α-Ara f units. Others were present at δ 175.4 from C-6 of α-Glc pA and δ 15.6 from C-6 of Fuc p units. The main chain of SPNa was confirmed by analysis of a Smith-degraded polysaccharide (SPDS): methylation analysis provided a 2,3-Me 2–Xyl (65%) derivative and its 13C NMR spectrum showed five main signals typical of a (1 → 4)-linked β-Xyl p units. Methylation analysis of a carboxy-reduced polysaccharide (SPN-CR) revealed a 2,3,4,6-Me 4–Glc derivative (4%) arising from nonreducing end-units of Glc pA. α-Glc pA-(1 → 2)-αβ-Xyl p and α-Glc pA-(1 → 2)-β-Xyl p-(1 → 4)-αβ-Xyl p were obtained via partial acid hydrolysis of SPN, showing the structure of side-chain substituents on O-2 of the main-chain units.