We demonstrate a simple, efficient, yet versatile strategy for the synthesis of novel hierarchical heterostructures composed of TiO2 nanofiber stem and various metal oxides (MOs) secondary nanostructures, including Co3O4, Fe2O3, Fe3O4, and CuO, by advantageously combining the versatility of the electrospinning technique and hydrothermal growth method, for which the controllable formation process and possible formation mechanism are also investigated. Moreover, as a proof-of-concept demonstration of the functional properties of these hierarchical heterostructures, the Co3O4/TiO2 hierarchical heterostructures are investigated as the lithium-ion batteries (LIBs) anode materials for the first time, which not only delivers a high reversible capacity of 632.5 mAh g(-1) and 95.3% capacity retention over 480 cycles, but also shows excellent rate capability with respect to the pristine TiO2 nanofibers. The synergetic effect between Co3O4 and TiO2 as well as the unique feature of hierarchical heterostructures are probably responsible for the enhanced electrochemical performance.