A nano-Si/FeSi2Ti hetero-structure has been synthesized for highly reversible Li-ion batteries by using a simple melt-spinning method. We demonstrate that this composite has a very peculiar core/shell structure in which the FeSi2Ti alloy plays various pivotal roles as a mechanically supporting backbone and as an electronic pathway for the active Si attached to its surface, and is responsible for the altered electrochemical reactions with relatively small volume expansion routes. The FeSi2Ti matrix significantly contributes to not only the stabilization of cyclic retention, but also the enhancement of conductivity, as well as a high rate capability unprecedented in research on Si-based anodes. This achievement demonstrates the potency of this novel hybrid design for electrode materials for energy storage.