Thin layered biomaterial surfaces of maleic anhydride copolymers are provided as a versatile platform for biomaterial applications. The provided comonomers define the character of the surface and its behaviour towards biomolecules and biosystems, such as proteins and cells. The kinetics of adsorption, desorption, and exchange of fibronectin and human serum albumin were investigated on different copolymer surfaces. Two different species of adsorbed proteins were found, a fast and a slow desorbing one. Furthermore, the exchange process depends on the kind of pre-adsorbed protein and the kind of exchange protein, as well as of the hydrophobicity of the copolymer surface. In this context adhesion, proliferation, and differentiation of endothelial cells from the umbilical cord vein onto fibronectin pre-coated surfaces were studied. Strong correlation between fibronectin exchange characteristics and the formation of focal adhesions, reorganisation of fibronectin, and generation of vascular-like structures by the cells was observed.