Surface concentration of cell adhesion peptides is thought to play a role in the interactions between biomaterials and cells. The high density of functional groups at the periphery of dendrimers has been exploited in various applications, but their full potential for generating surfaces with high functional group concentrations has not yet been realized. Poly(dimethylsiloxane) elastomers were surface modified with both Polyethylene oxide (PEO) and generation 3 diaminobutane dendrimers. PEO and the dendrimers were subsequently used as linker molecules for surface grafting of cell adhesion peptides. ATR-FTIR, X-ray photoelectron spectroscopy, and water contact angle results confirmed the successful attachment of the polymer linkers and peptides. Peptide grafting density was quantified by means of 1251 radiolabeling. Maximum surface peptide grafting density on dendrimer-modified surfaces was twofold greater than the maximum peptide grafting density achieved via the PEO linker. However, vascular endothelial cell adhesion was significantly greater on surfaces modified with the PEO linker, presumably due to the highly flexible EO spacer making the peptide more accessible for binding with the cell surface receptors. These results suggest that, although peptide surface density may be important, optimizing surface density may not be sufficient for improving biological interactions.