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Skin tissue engineering with considerable skin regeneration capability is an urgent need for the wound site. The current challenge for researchers is to develop a bionic scaffold that imitates the extracellular matrix for the regeneration of the damaged regions. In our study, poly(L-lactide-co-caprolactone) (PLCL) was blended with polyurethane (PU) to obtain nanofibrous scaffolds via electrospinning. The electrospun fibers with 50% PLCL content had a certain number of intersections and jointing points, and exhibited significantly enhanced mechanical properties combined with suitable porosity. Moreover, cell activities demonstrated that PU/PLCL membranes had significantly biological advantages in enhanced growth of human skin fibroblasts with spreading morphology compared with PU membranes, indicating good cytocompatibility of composite scaffolds. These findings proved that PU/PLCL electrospun membranes have great potential in applications of skin tissue engineering.