Polymer blending is one of the most effective methods for providing new, desirable biocomposites for tissue-engineering applications. In this study, electrospun poly(L-lactide)/poly(epsilon-caprolactone) (PLLA/PCL) blend fibrous membranes with defect-free morphology and uniform diameter were optimally prepared by a 1 : 1 ratio of PLLA/PCL blend under a solution concentration of 10 wt %, an applied voltage of 20 kV, and a tip-to-collector distance of 15 cm. The fibrous membranes also showed a porous structure and high ductility. Because of the rapid solidification of polymer solution during electrospinning, the crystallinity of electrospun PLLA/PCL blend fibers was much lower than that of the PLLA/PCL blend cast film. To obtain an initial understanding of biocompatibility, adipose-derived stem cells (ADSCs) were used as seed cells to assess the cellular response, including morphology, proliferation, viability, attachment, and multilineage differentiation on the PLLA/PCL blend fibrous scaffold. Because of the good biocompatibility and nontoxic effect on ADSCs, the PLLA/PCL blend electrospun fibrous membrane provided a high-performance scaffold for feasible application in tissue engineering using ADSCs. (C) 2010 Wiley Periodicals, Inc. J Appl Polym Sci 120: 2154-2165, 2011