Aims Bacterial lipopolysaccharide (LPS) protruding from the outermost layer of the outer membrane is expected to play an important role in cell physiology by interacting with molecules in the extracellular milieu; however, the structural and functional characteristics of these components in cyanobacteria remain largely unknown. We isolated water-soluble fractions of LPS and O-chain from the bloom-forming freshwater cyanobacterium Microcystis aeruginosa NIES-87 and identified their monosaccharide compositions. Methods and Results SDS-PAGE followed by silver staining demonstrated that the isolated total LPS was the smooth type with different numbers of repeating sugar units in the O-chain region. GC/MS analysis after acid hydrolysis, reduction and acetylation treatments indicated that the neutral monosaccharide components of the total LPS include glucose, rhamnose, mannose, galactose and xylose (in decreasing order of weight percentage), while only glucose was detected in the purified O-chain fraction. MALDI-TOF MS analysis suggested that the O-chain fraction is composed of repeating glucose and methylated glucose disaccharide units. Conclusions Our results indicate that the monosaccharide composition of M. aeruginosa O-chain is relatively simple. Significance and Impact of the Study Although further studies are necessary, these findings provide fundamental information for understanding the structural and functional properties of cyanobacterial LPS and O-chain.