The O-antigenic polysaccharide of Salmonella Mara O:39 (formerly Q) was investigated by sugar and methylation analyses, absolute configuration assignment, mass spectrometry and NMR spectroscopy. The experiments revealed an O-polysaccharide chain composed of the following linear tetrasaccharide repeating units with the structure: -->2)-alpha-L-Quip3NAc-(1-->3)-alpha-D-Manp-(1-->3)-alpha-L-Fucp-(1-->3)-alpha-D-GalpNAc-(1--> where alpha-L-Quip3NAc is the residue of 3-acetamido-3,6-dideoxy-alpha-L-glucopyranose. This repeating unit is the first published structure of the O-polysaccharide from 27 serotypes of Salmonella bacteria belonging to serogroup O:39 in the Kauffmann-White classification system.