To design high performance SiO2-based anodes for Li-ion batteries (LIBs), an amorphous SiO2-FeSi-graphite (a-SiO2/FeSi/G) composite was synthesized by a simple solid state synthetic method using SiO, Fe, and graphite powders. The a-SiO2/FeSi/G composite was comprised of well dispersed amorphous SiO2 and tiny (5–10 nm sized) FeSi inactive matrices within the graphite buffering matrices. The a-SiO2/FeSi/G composite electrode showed excellent electrochemical performance featuring high initial charge capacity of 729 mAh g−1, with high initial Coulombic efficiency of approximately 74%, and long capacity retention of 93.7% after 200 cycles, with a highly reversible capacity of 683 mAh g−1.