The major fraction of rhamnogalactan was isolated from the cell wall of Bifidobacterium longum YIT4028 by treatment with N-acetylmuramidase. This polysaccharide was composed of rhamnose and galactose in a molar ratio of about 2:3. The 13C NMR spectrum indicated that it contained a pentasaccharides repeating unit. This observation, and the results of Smith degradation, partial acid hydrolysis and methylation analysis led to the conclusion that its structure is [formula: see text]