A polysaccharide from the leaves of Sesamum radiatum was extracted by maceration in deionized water followed by ethanol precipitation then chemically and physically characterised. Monosaccharide composition and linkages were determined by high performance anion exchange chromatography (HPAEC), gas chromatography–mass spectrometry (GC–MS) and nuclear magnetic resonance (NMR) spectroscopy respectively. Sesamum gum was composed of glucuronic acid, mannose, galactose, and xylose with trace quantities of glucose, rhamnose and arabinose. Proton and 13C NMR spectroscopy, and linkage analysis revealed a glucuronomannan based structure comprising a backbone of →4)-β-D-GlcpA-(1 → 2)-α-D-Manp-(1→ with side-chains of galactose and xylose. Hydrated sesamum gum displayed temperature independent viscoelastic properties with no thermal hysteresis. Intrinsic viscosity was determined to be 3.31 and 4.40 dL g−1 in 0.1 M NaCl and deionised water respectively, while the critical concentration was determined to be 0.1% w/v. The characterisation performed in this study will help direct potential applications of this material in foods and pharmaceuticals.