A novel binder-free reduced graphene oxide/silicon (RGO/Si) composite anode has been fabricated by a facile doctor-blade coating method. The relatively low C/O ratio plays an important role for the fabrication of the bind-free multilayered RGO/Si electrode with silicon nanoparticles encapsulating among the RGO sheet layers. The RGO provides the electron transport pathway and prevents the electrode fracture caused by the volume changes of active silicon particles during cycling. The RGO/Si composite anode with a silicon content of 66.7% delivers a reversible capacity of 1931 mAh g−1 at 0.2 A g−1 and still remains 92% of the initial capacity after 50 cycles.