Nerve guidance conduits (NGCs) must have favorable biological and mechanical properties for peripheral nerve repair applications. In this study, we developed a composite structure of electrospun silk fibroin-based NGCs (SF-NGCs) through three step procedures. The unique structure was formed by embedding SF-based reinforcing network in a simple electrospun SF-NGC, thus leading to additional compressive strength and suture retention strength. These complex electrospun SF-NGCs were implanted to bridge a 10-mm long sciatic nerve defect in rats. Histological and functional assessments were performed at 6 months after nerve grafting. Results of examined functional and morphological parameters showed that these complex electrospun SF-NGCs promoted peripheral nerve regeneration because electrospun nanoporous SF fibers were responsible for their good biological properties and an embedded reinforcing network enhanced their mechanical properties. The study suggested that the prepared SF-NGCs may be new type of tissue-engineered nerve grafts for peripheral nerve repair.