Abstract: A binder-free silicon-carbon nanofiber-graphene (Si-CNF-G) hybrid membrane was prepared by embedding Si particles encapsulated in a porous carbon in a cobweb-like carbon scaffold composed of CNFs and G nanosheetsproduced using the coaxial electrospraying method. The binder-free Si-CNF-G electrode delivered an initial reversible specific capacity of 957 mAh·g^-1 with a retention of 74.4% after 100 cycles at 0.2 A·g^-1, and a rate capability of 539 mAh·g^-1 at 2 A·g^-1, which was much better than that of a Si electrode. This can be attributed to the fact that the porous carbon matrix was able to buffer the large volume expansion and contraction of Si during charging and discharging, and that the interconnected carbon scaffold not only created efficient pathways for electron conduction and ion transfer, but also improved the structural stability of the whole electrode.