Vascular grafts made of expanded polytetrafluoroethylene (ePTFE) are widely employed in vascular reconstructive surgery. While they are successful as replacements for large-diameter blood vessels, ePTFE vascular grafts are unsuitable for small-diameter ones because when the internal diameters of the graft are less than 6 mm, they are found to fail without exception due to blood clot formation. To reduce platelets adhesion onto the ePTFE vascular graft, a novel method of binding of chitosan/heparin (CS/Hp) complex to the surface of vascular graft was developed. The binding of chitosan was achieved by irradiating with ultraviolet light the azide modified chitosan that was coated on the ePTFE surface. By forming complex with this coating of chitosan, heparin was then bonded to the ePTFE surface. In vitro blood compatibility experiments showed that CS/Hp surface-modified ePTFE vascular grafts exhibited markedly reduced platelets adhesion. The outstanding performance of these grafts was further demonstrated by the in vivo experiments, in which they were found to be still unclogged two weeks post-implantation into dog veins. (C) 2004 Elsevier B.V. All rights reserved.