The nanofibrous silk scaffolds with good biocompatibility and minimal immunogenicity exhibited promise in the tissue engineering. However, the utilization of silk fibroin (SF) is hampered by the poor mechanical properties of regenerated SF. Suitable SF alloys would allow for an improvement in the mechanic properties of the SF. Therefore, SF/poly(epsilon-caprolactone) (PCL) biomimetic scaffolds were prepared to develop an extracellular matrix (ECM) nanofibrous architecture by electrospinning for potential application in peripheral nerve injury. The mechanical properties of the SF/PCL scaffolds were significantly improved compared with SF scaffold. The degradation rate of the SF/PCL scaffold could be controlled by changing the ratio of SF to PCL. Blending SF with PCL could not only retain the biocompatibility of SF, but also bring the superior mechanical and controlled biodegradability, suggesting their promising future for peripheral nerve tissue engineering.