A facile strategy was designed for the fabrication of Fe3O4-nanoparticle-decorated TiO2 nanofiber hierarchical heterostructures (FTHs) by combining the versatility of the electrospinning technique and the hydrothermal growth method. The hierarchical architecture of Fe3O4 nanoparticles decorated on TiO2 nanofibers enables the successful integration of the binary composite into batteries to address structural stability and low capacity. In the resulting unique architecture of FTHs, the 1D heterostructures relieve the strain caused by severe volume changes of Fe3O4 during numerous charge-discharge cycles, and thus suppress the degradation of the electrode material. As a result, FTHs show excellent performance including higher reversible capacity, excellent cycle life, and good rate performance over a wide temperature range owing to the synergistic effect of the binary composition of TiO2 and Fe3O4 and the unique features of the hierarchical nanofibers.