We demonstrate a simple, efficient, yet versatile strategy for the synthesis of novel TiO2/Fe2O3 fiber-in-tube hierarchical heterostructures by using a simple electrospinning technique and subsequent annealing. The mechanism for the formation of these controllable structures is investigated. When tested as the anode materials in lithium-ion batteries (LIBs), the TiO2/Fe2O3 fiber-in-tube hierarchical heterostructures not only deliver a high reversible capacity of 987.2 mA h g(-1), which is almost quadruple that of the pure TiO2 nanofibers, and 65.1% capacity retention over 240 cycles, but also show excellent rate capability due to the synergetic effect between Fe2O3 and TiO2 as well as the unique features.