Haemocompatible new urethane copolymers and polymer blends containing, in the chain extender, a long chain alkyl group (able to bond albumin) or a tertiary ammonium group able, after suitable quaternization reaction, to bind ionically significant amounts of heparin, were prepared. The copolymers were characterized by differential scanning calorimetry, intrinsic viscosity determinations, infrared spectroscopy and nuclear magnetic resonance (1H and 13C). Biological in vitro evaluation has shown that the adsorption sequence for albumin and heparin, respectively, onto films of the various copolymers and blends, exerts a great influence. From scanning electron microscopy measurements it was seen that the bonding type of albumin to the polymer films plays a determining role on the platelet activation. A phase segregation occurring on the polymer blends surface was demonstrated by X-ray photoelectron spectroscopy measurements.