A SiO2/C composite was obtained by modifying biomass rice husk ash (RHA) with ball milling, followed by mixing with coal tar electrode pitch (CTEP) and pyrolyzing under high temperature. The modified SiO2/C material gained a significant improvement in electrochemical performance, including cycle performance, initial Coulombic efficiency (ICE) and electrical impedance. Meanwhile, it maintained a good reversible specific capacity of 404 mA h g−1 over 500 cycles at the current density of 0.25 C. Therefore, the modification method provides a potential for offsetting defects and promoting electrochemical performance of biomass-based anode materials of lithium ion batteries (LIBs).