Carbon nanofibers encapsulating Si nanoparticles (CNFs/SiNPs) were prepared via an electrospinning method and chemically functionalized with 3-aminopropyltriethoxysilane (APS) to be grafted onto graphene oxide (GO). As a result, the thin and flexible GO, which exhibits negative charge in aqueous solution, fully wrapped around the APS-functionalized CNFs with positive surface charge via electrostatic self-assembly. After forming chemical bonds between GO and the amine groups in APS via epoxy ring opening reaction, the GO was chemically reduced to a reduced graphene oxide (rGO). Electrochemical and morphological characterizations showed that capacity loss by structural degradation and electrolyte decomposition on Si surface were significantly suppressed in the rGO-wrapped CNFs/SiNPs (CNFs/SiNPs@rGO). Superior capacities were consequently maintained for up to 200 cycles at a high current density (1048 mAh g-1 @ 890 mA g-1) compared to CNFs/SiNPs without the rGO wrapping (304 mAh g-1 @ 890 mA g-1). Moreover, thickness of the SEI layer and charge transfer resistance were also greatly reduced by 24% and 88%, respectively. The graphene wrapping offers a versatile way to enhance the mechanical integrity and electrochemical stability of Si composite anode material.