A boron (B)-polysaccharide complex was isolated from a Driselase digest of sugar beet ( Beta vulgaris L.) cell walls by ion-exchange and gel-permeation chromatography. The complex contained 0.12% B (w/w). The polysaccharide moiety contained 2- O-methylfucose, rhamnose, fucose, 2- O-methylxylose, arabinose, apiose, galactose, aceric acid, galacturonic, and glucuronic acids residues, and thiobarbituric acid-assay positive sugars, presumably 3-deoxy- d-manno-2-octulosonic acid (Kdo) and 3-deoxy- d- lyxo-2-heptulosaric acid (Dha). Methylation analysis, together with glycosyl composition analysis, showed that the polysaccharide was a typical rhamnogalacturonan-II (RG-II), a structurally complex pectic polysaccharide present in the primary cell walls of plants. 11B NMR spectroscopy showed that the B was present as a tetrahedral borate-diol diester. Approximately 70% of B was released by treating the B—RG-II complex at pH 4.8 at 40 °C.