Commercial crude fucoidan (Sigma) from the brown seaweed Fucus vesiculosus was fractionated into its polysaccharide components by gel filtration and anion-exchange chromatography to clarify the structure-anticoagulant activity relationship. The products comprised a wide spectrum of fucans ranging from typical fucoidans (major components) containing mainly fucose, sulfate, and no uronic acid to low sulfate-containing heteropolysaccharide-like fucans (minor components) being composed of neutral sugars other than fucose and a high content of uronic acid(s). The polysaccharide components also had a wide range of molecular weight. The typical fucoidans showed a potent anticoagulant activity, whereas the other fucans had no or only slight activity. One of the fractions found as a minor component, was a novel polysaccharide containing an appreciable amount (11.5%) of glucosamine and a small amount (5.2%) of protein in addition to fucose and sulfate, and having a low apparent molecular weight of 6800. This is the first report that a proteoglycan-like, amino sugar-containing fucan sulfate, composed of fucose, galactose, glucose, mannose, xylose, uronic acid, glucosamine, and sulfate in the molar ratio of 1.00:0.04:0.01:0.48:0.24:0.18:0.56:1.90, could be obtained from brown seaweed. However, this polysaccharide showed no anticoagulant activity.