Novel silicon@ carbon/carbon nanotubes&carbon nanofibres (Si@C/CNTs&CNFs) composites have been successfully synthesized by a serious of high-energy wet ball milling, closed spray drying and subsequently chemical vapor deposition methods, in which carbon nanotubes and carbon nanofibers are interweaved with carbon coated silicon (Si@C) spherical composites. As anode materials for lithium-ion batteries, the Si@C/CNTs&CNFs composites demonstrate a high first discharge capacity and excellent cycle ability. The high initial specific discharge capacity is approximately 2169mAhg−1 and a reversible specific capacity approached 1195mAhg−1 after 50cycles at a high current density of 300mAg−1.