Ordered porous Si@C nanorods as anode materials for high-performance lithium-ion batteries were prepared via two-step approaches, including magnesiothermic reduction of well-ordered hexagonal mesoporous silica (SBA-15) and impregnating of carbon precursor into the mesoporous Si followed by carbonization. The obtained porous Si@C nanorods demonstrate a reversible specific capacity approaching 627mAhg−1 after 220 cycles at a rate of 100mAg−1 as well as improved cycling stability and excellent rate capacity. The improved electrochemical performance can be attributed to the fact that the porous interwoven structure of conductive carbon and Si composite can efficiently suppress the volume effect of the Si particles and increase the electronic conductivity. The porous Si@C nanorods exhibit a great potential as anode materials in lithium ion batteries.