Silicon-based anode materials are indispensable components in developing high energy density lithium-ion batteries, yet their practical application still faces great challenges, such as large volume change during the lithiation and delithiation process that causes the pulverization of silicon particles, and continuous formation and reformation of the solid electrolyte interfaces (SEI) which results in a low initial coulombic efficiency. As an endeavor to address these problems, in this study, Si/SiO/Li2SiO3@C structures were prepared via a facile method using SiO, pitch powder and Li2CO3/PVA solution followed by annealing treatment. The Si/SiO/Li2SiO3@C composite shows a great improvement in lithium storage where a high discharge capacity of 1645.47 mA h g−1 was delivered with the 1st C.E. of 69.05% at 100 mA g−1. These results indicate that the designed method of integrating prelithiation and carbon coating for SiO and the as-prepared macro scale Si/SiO/Li2SiO3@C structures are practical for implementation in lithium-ion battery technology.