Inferior cycling stability and rate performance respectively caused by rigorous volume change and poor electrical conductivity were the main challenge of state-of-the-art Silicon-based electrode. In this work, silylated functionalized exfoliated graphite oxide (EGO)/silicon@amorphous carbon (3-APTS-EGO/Si@C) was synthesized by adopting silane as intermediate to connect Si particles with EGO sheets followed by introduction of amorphous carbon. The result suggested that 3-Aminopropyltriethoxysilan connected the EGO sheets and Si nanoparticles via covalent bonds. Owing to the strong covalent interaction and the synergistic effect between the silicon, EGO sheets and amorphous carbon, 3-APTS-EGO/Si@C composite possessed a high capacity of 774 mAh g−1 even after 450 cycles at 0.4 A g−1 with the retention capacity of 97%. This work also provided an effective strategy to improve the long cycling life performance of Si-based electrode.