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Design of polymeric scaffolds with specific physical and biological properties is a key objective of tissue engineering research. In this work, a novel copolymer poly (ε-caprolactone)-b-poly(carboxybetaine methacrylate) (PCL-PCBMA) containing zwitterion and polyester segments, was synthesized through ATRP technique. The chemical structure,composition,and molecular weight of the synthesized copolymer were characterized by 1HNMR and GPC. The polymer was further electrospun into fibrous film which has been characterized by SEM, XPS, water uptake test, and MTT cell culture assay. All these results indicate that this kind of copolymer is a suitable candidate for the application in vascular tissue engineering.