Glycosaminoglycan constituents of the periodontium have been detected in supragingival and subgingival dental calculus. They are polyanionic heteropolysaccharides containing -COOH and SO 3 H residues. The non-sulfated hyaluronan is present in supragingival calculus, whereas chondroitin sulfate, dermatan sulfate, and heparan sulfate are detected in subgingival calculus. They are implicated in both ectopic and endogenous mineralization, and have been used in the present study to investigate seeded hydroxyapatite crystal growth, and the influence of fluoride on the process. All glycosaminoglycans examined inhibited crystal growth, with chondroitin-4-sulfate and dermatan sulfate being more effective than the hyaluronan. Fluoride alone enhanced growth and reduced the inhibitory influence of the glycosaminoglycans and the parent proteoglycan, which is a potent inhibitor. The results yield important information on the role of fluoride and proteoglycan in ectopic mineralization.