The sulfated glycosaminoglycans (sGAG) heparin and chondroitin sulfate (CS) were immobilized on the surfaces of gold nanorods as part of a polyelectrolyte multilayer. The effects of these nanomaterials on the self-assembly of type I collagen were examined by turbidity assays and microscopy, and desorption of sGAG from nanomaterial-collagen composites was quantified biochemically. The interactions of sGAG-coated nanorods with cardiac cells were also explored through a collagen gel contraction assay and confocal microscopy. In contrast to soluble forms of sGAG, sGAG-coated nanorods consistently accelerated collagen fibrillogenesis. Soluble heparin, and heparin-and CS-coated nanorods inhibited cell-mediated contraction of collagen gels, whereas soluble CS did not. Both heparin and CS-coated nanorods were detected in the peri-and/or intra-cellular compartments of the cells, but there was no evidence of cytotoxicity over 72 h of culture. These results indicate that biological polyanions, such as sGAG, may be useful in the modification of nanoparticle surface chemistry for biological and/or therapeutic applications.