Novel sandwich-structured silicon-based anodes have been prepared to inhibit the fragmentation of silicon electrodes typically caused by the large volume changes that occur during charge/discharge processes. An electrostatic self-assembly method and hydrothermal dehydration are used to introduce a reduced graphene oxide layer (rGO) on the surface of silicon/carbon nanofibers (Si/CNFs), which prevent the exfoliation of nano-Si from the electrode bulk to the liquid electrolyte, reduce the electric contact loss, stabilize the electrode’s structural integrity, and improve electrochemical conductivity. The Si/CNFs@rGO exhibit superior electrochemical performance as an anode, retaining a high specific capacity of 1055.1mAhg−1 up to 130 cycles at 0.1Ag−1, with slight capacity loss. The Si/CNFs@rGO electrode also demonstrates outstanding rate behavior with a reversible capacity of 358.2mAhg−1 at 5Ag−1. Results indicate that the graphene layer significantly improves the electrochemical performance of the silicon/carbon nanofiber electrode.