Electrospun fiber mesh has been a candidate for guided bone regeneration membrane. However, its poor mechanics property has been limited in clinical application. In this study, various star-shaped poly(epsilon-caprolactones) (PCLs) are successfully synthesized by ring-opening polymerization and mixed with poly(l-lactide) (PLLA) to be made into blended membranes through electrospinning. Their corresponding properties are evaluated including morphology, thermodynamics, mechanics, and cytotoxicity. The blended fibers show smooth surface and well-distributed structure, which have slight differences in morphology with the change of arm number of star-shaped PCL. Crystallization of the fibrous membrane is influenced by star-shaped PCLs. Glass temperature drops from 64.23 degrees C for pure PLLA membrane to 53.62-49 degrees C for the blended membranes. The membranous tensile strength is depended strongly on star-shaped PCLs. The tensile strength goes up with arm number increasing; on the contrary, at the same arm number, the mechanics strength decreases with molecular weight increasing. And the fibrous membrane containing 20 wt.% star-shaped PCL shows better mechanics property compared to the other membranes. The star-shaped PCL/PLLA fiber membrane is not cytotoxicity.