Four-arm star-shape poly(ε-caprolactone)s were prepared by Ring Opening Polymerization(ROP) with pentaerythritol/Stannous octoate as the initiator system. Photocurable and heparinized four-arm star-shape poly(ε-caprolactone) (PCL) was synthesized by covalently attaching acryloyl chloride and heparin to the ends of four-arm star-shape poly(ε-caprolactone)s. The resulting polyester was also cross-linked under UV light with good mechanical properties. The properties of the four-arm star-shape poly (ε-caprolactone)s were tested by using GPC, IR and 1H-NMR. The results of static contact angle and water absorption show that this heparinized PCL has better hydrophilic quality than its counterpart. The heparin content on the surface of this PCL was characterized by UV. The anticoagulant characteristics in vitro were evidenced by APTT test and the time of APTT test was obviously prolonged. The results of APTT test show that the heparinized material enjoys anticoagulant properties. The resulting polyester may also be cross-linked under UV light by adding an appropriate amount of photo-initiator. The results of mechanical tests show that the tensile strength is improved significantly after the exposure to the UV light. A preliminary study on its electrospinning properties was also carried out. The material can successfully be electrospun into tubular scaffolds with an ultrafine fiber structure. The cross-linked and anticoagulant heparinized four-arm star-shape poly (ε- caprolactone) enjoys a good application prospect in the field of vascular tissue engineering.