SnO2/α-Fe2O3 hybrid nanofibers, consisting of one dimensional hollow SnO2 nanotubes decorated with Fe2O3 particles, are synthesized via a facile electrospinning process followed by a hydrothermal treatment and investigated as the anode material for lithium-ion batteries. The SnO2/Fe2O3 hybrid nanofibers not only provide a large surface area for lithium storage sites, but also show the capability of fast charge transport for both electrons and lithium ions. Both SnO2 and Fe2O3 contribute to the lithium storage and the hybrid structure exhibits a synergistic effect when participating in electrochemical reactions. With the smart structure design, the hybrid SnO2/Fe2O3 nanofiber electrode shows superior electrochemical performance compared to the bare SnO2 nanofiber electrode. In addition to a large first-cycle discharge capacity up to 1105 mAh g-1, the hybrid SnO2/Fe2O3 nanofibers electrode also exhibits good cycling stability and high rate capability.