The affinities for hyaluronic acid of newly synthesized proteoglycan from post-confluent rabbit chondrocyte cultures and purified bovine proteoglycan monomer were compared. In mixtures prepared at pH 6.8 the newly synthesized proteoglycan had the lower affinity; however, in mixtures incubated at pH 8.5 for 24 h before addition of hyaluronic acid, the newly synthesized proteoglycan exhibited a markedly higher affinity than the bovine monomer. The results suggest that proteoglycan secreted without associated link protein [Plaas, Sandy & Muir (1983) Biochem. J. 214, 855-864] has a low affinity for hyaluronate and that this may be increased during subsequent extracellular processing.