Using sugar and methylation analyses, and one- and two-dimensional 1H-NMR spectroscopy at 500 MHz it was established that poly-β-1,2-4-deoxy-D-arabinohexopyranose occurs as O-specific chains of lipopolysaccharides in Citrobacter serotypes O4, O27 and O36. Strong serological cross-reactivity between these serotypes is in full agreement with the chemical identity of their O-specific polysaccharides.