Poly(ethylene oxide) (PEO) polymer, in Linear and star form, was covalently grafted to silicon surfaces, and the surfaces were tested for their ability to adsorb proteins. Linear PEG of molecular weight 3400, 10 000, and 20 000 g/mol and star PEO molecules were coupled via their terminal hydroxyl groups activated by tresyl chloride to aminosilane-treated silicon wafers. The amount of PEO coupled to the surface was varied by changing the concentration of the tresyl-PEO solution. The dry PEO thickness on the surface was measured using X-ray photoelectron spectroscopy (XPS) and ellipsometry, from which the grafting density was calculated. The PEO surfaces were exposed to solutions of each of three proteins : cytochrome-c, albumin, and fibronectin. The degree of adsorption of each protein was determined by XPS and ellipsometry and recorded as a function of PEO grafting density. All three proteins were found to reach zero adsorption at the highest grafting densities on all three PEG surfaces, which for all three PEG surfaces was a PEO content of 100 +/- 10 ng/cm(2). On both star PEO surfaces, albumin and fibronectin decreased to zero adsorption at intermediate values of grafting density, whereas cytochrome-e continued to adsorb at all grafting densities, although with a decreasing trend. A physical model of the surface helped explain these protein adsorption results in terms of the spacing and degree of overlap of grafted PEO chains.