Vibriosis caused by Vibrio anguillarum affects salmonid and marine fish species worldwide and is considered to be one of the most serious threats to the success of commercial fish farming. In the course of this study, it was found that V. anguillarum serotype O:2 strains produce an acidic capsular polysaccharide having the identical structure to that of the O-chain polysaccharide. One-dimensional and two-dimensional nuclear magnetic resonance techniques, together with partial hydrolysis and various specific modifications, were used to determine the structure of these polysaccharides. It is proposed that both O-chain and capsular polysaccharide of V. anguillarum serotype O:2 are composed of linear tetrasaccharide repeating units having the following structure, in which Glc2NAc3NAN represents 2-acetamido-3-amino-2,3-dideoxy- d-glucuronamide, Man2NAc3AmA is 3-acetamidino-2-acetamido-2,3-dideoxy- d-mannuronic acid, Am represents an acetamidino group, Gal(NAc) 2A is 2,3-diacetamido-2,3-dideoxy- l-galacturonic acid, Bac(NAc) 2 is 2,4-diacetamido-2,4,6-trideoxy- d-glucose ( N, N′-diacetylbacillosamine) and Fo is formyl. ▪