Simusan, a major exopolysaccharide produced by an ethanol-utilizing Arthrobacter sp. strain CE-17, contains D-glucose, D-mannose, D-galactose, L-rhamnose, D-glucuronic acid, and pyruvic acid in the ratios approximately 3:2:1:1:1:1 as well as O-acyl groups (presumably (presumably residues of acetic and palmitic acid). On the basis of chemical modifications of the polysaccharide, solvolysis with anhydrous hydrogen fluoride resulting in a penta- and an octa-saccharide fragment, Smith degradation, and 1H and 13C NMR analysis, the following structure of the repeating unit was established: [formula: see text] It is suggested that at least one of the glucose residues and the galactose residue are O-acetylated.