To create novel materials of skin tissue engineering, the blends of tannin-grafted poly(E >-caprolactone) (TA-g-PCL) and poly(l-lactic acid) (PLLA) have been prepared by electrospinning, and their corresponding characteristics are evaluated such as morphology, FTIR, thermodynamics, mechanics, wettability, as well as biocompatibility. TA-g-PCL and PLLA can be well blended to make smooth fibers, and fibrous diameter turns thinner with blending TA-g-PCL. At 15 wt%, the fibrous membrane shows higher tensile strength and elongation at a break than the other samples due to its best crystallinity. Membranous wettability drops with blending TA-g-PCL, but it increases sharply after incorporating PF108. At the same time, PLLA/TA-g-PCL fiber membrane is biocompatible. The biodegradable PLLA/TA-g-PLLA membrane is a promising candidate as skin tissue engineering.