The hypothesis that the adhesion of whole cancer cells to glycosaminoglycan (GAG) substrates is a function of polysaccharide radius of gyration is presented. We use a worm-like chain (WLC) polymer model describing the global structure of the GAGs that will take into account the charge distribution and contour length of the polysaccharide implicitly in its radius of gyration to relate these parameters to cell adhesion. Specifically, we present measurements of the in vitro adhesion of cancer cells to isolated and individualized GAG substrates. We find that adhesion of the cells has a linear response with the radius of gyration and is essentially controlled by the charge per dimer. This dominating mechanism is not eliminated when the cells are subjected to resuspension in media with heparin. We then propose how these physical properties could be used to predict the preferred molecular structures of compounds for use as antimetastatic or antiinflammatory agents by comparing our results with known effective molecules. (C) 2008 Wiley Periodicals, Inc. J Appl Polym Sci 111: 70-77, 2009