The structure of an exopolysaccharide (EPS) produced by Burkholderia brasiliensis, a diazotrophic endophytic organism originally isolated from rice roots, has been determined. The bacterium was grown in a synthetic medium, containing mannitol and glutamate, which favours the expression of two anionic EPSs, which were separated by anion-exchange chromatography. The structure of the repeat unit of EPS A, eluted at higher ionic strength, was determined by a combination of methylation analysis, partial hydrolysis, chemical degradations, and NMR spectroscopic studies, and shown to be the linear O-acetylated pentasaccharide: -->4)-alpha-D-Glcp-(1-->2)-alpha-L-Rhap-(1-->4)-alpha-D-GlcpA-(1-->3)-beta-L-Rhap[2OAc]-(1-->4)-beta-D-Glcp-(1-->.