Advanced SiO2–carbon composite anode active material for lithium-ion battery has been synthesized through a simple chelation of silicon cation with citrate in a glyme-based solvent. The resultant composite material demonstrates a homogeneous distribution of constituents over the submicron particles and a unique hollow spherical microstructure, which provides an enhanced electrical conductivity and better accommodation of volume change of silicon during electrochemical charge–discharge cycling, respectively. As a result, the composite electrode exhibits a high cycling stability delivering the capacity retention of 91% at the 100th cycle and discharge capacities of 662–602mAh/g and coulombic efficiencies of 99.8%. This material synthesis is scalable and cost-effective in preparing various submicron or micron composite electrode materials.