The structure of the O-antigenic polysaccharide from Escherichia coli O167:H5 has been investigated. Sugar and methylation analyses, fast-atom-bombardment mass spectrometry and H-1- and C-13-NMR spectroscopy were the main methods used. The structure of the repeating unit of the polysaccharide was found to be: [GRAPHICS] Oligosaccharide derivatives of the polysaccharide were obtained by HF solvolysis and by a Smith degradation. Furthermore, base treatment of the polysaccharide led to a degraded polymeric material. For the methylated polysaccharide the amide linkage between alanine and the galacturonic acid residue was reductively cleaved with LiBD4 in ethanol, to give, among other things, a 3-O-methyl galactose derivative.