The initial response of blood exposed to an artificial surface is the adsorption of blood proteins that triggers a number of biological reactions such as inflammation and blood coagulation. Competitive protein adsorption plays a key role in the hemocompatibility of the surface. The synthesis of nonfouling surfaces is therefore one of the major prerequisites for devices for biomedical applications. Polysaccharides are the main components of the endothelial cell glycocalyx and have the ability to reduce nonspecific protein adsorption and cell adhesion and, therefore, are generally coupled with a wide variety of surfaces to improve their biocompatibility. We have developed a procedure for covalently binding dextran and sodium hyaluronate (HA) on silicon wafers and we have been able to achieve a high level of control over the surface properties of the coatings. In the present research effort we focus on a detailed investigation of competitive bovine serum albumin (BSA) and bovine fibrinogen (Fg) adsorption on dextran- and HA-modified silicon surfaces. Polysaccharide based biomimetic layers preferentially adsorb BSA and, in general, strongly suppress protein adsorption with respect to bare silicon and APTES-activated silicon surfaces used as control.