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Several invertebrate species contain variable amounts of one or more types of sulfatedglycosaminoglycans (GAGs). At present it is well known the existence of a species-specific sulfatedGAGs composition based on the relative amount and type of chondroitin sulfates, heparan sulfateand heparin. Heparin is a sulfated polysaccharide belonging to the family of GAGs with numerousimportant biological activities, such as anticoagulant and antithrombotic properties that derive from itsinteraction with diverse proteins. Unusual heparin samples for molecular mass, fine structuralorganization and anticoagulant activity, are isolated and characterized from molluscs. Variablepresence of the trisulfated disaccharide [DUA2S(1->4)-a-D-GlcN2S6S] and significant modifications ofthe disaccharides bearing non-sulfated iduronic and glucuronic acids, [->4)-a-L-IdoA(1->4)-a-DGlcNAc6S(1-> and ->4)-a-L-IdoA(1->4)-a-D-GlcN2S6S(1->] and [->4)-b-D-GlcA(1->4)-a-DGlcN2S6S(1->], and oligosaccharide sequences bearing part of the ATIII-binding region,[DUA2S(1->4)-a-D-GlcN2S6S(1->4)-b-D-GlcA(1->4)-a-D-GlcN2S3S6S] and [DUA2S (1->4) -a-DGlcN2S6S(1->4)-a-L-IdoA (1->4)-a-D-GlcNAc6S (1->4)-b-D-GlcA (1->4)-a-D-GlcN2S3S6S], aredetected and measured in heparin samples derived from different clam species. This review morespecifically deals with structural and biologically important aspects of heparin in invertebrates withspecial emphasis on the heparin from molluscs. Furthermore, the fine characterization of heparinfrom Tapes phylippinarum and Callista chione is reported.