Based on sugar and methylation analyses, O-deacetylation, Smith degradation, and 1H and 13C NMR spectroscopy, including 2D COSY, 1H-detected 1H, 13C heteronuclear single-quantum coherence (HSQC), and 1H-detected 1H, 13C heteronuclear multiple-bond connectivity (HMBC) experiments, the following structure of the O-specific polysaccharide of Proteus penneri strain 25 was established: [formula: see text] where D-GlcN(L-Ala) is 2-(L-alanylamido)-2-deoxy-D-glucose.