An amphiphilic block copolymer, poly(ε-caprolactone)-b-poly (sulfobetaine methacrylate), (PCL-b-PSBMA), which comprising of hydrophobic polyester segment and hydrophilic zwitterionic segment, was synthesized by ringopening polymerization (ROP) together with atom transfer radical polymerization (ATRP). The chemical structure and composition of the synthesized copolymers were first investigated by 1 HNMR and GPC. The copolymers were further processed into non-woven fabrics by electrospinning. The surface chemical composition, fiber morphology, hydrophilic/hydrophobic property, and cell viability of the as-prepared scaffold were evaluated by X-ray photoelectron spectroscopy, SEM, water contact angle and uptake measurement, and MTT assay, respectively. All these results indicate that this kind of copolymers is a suitable candidate for the biomedical application.