Transition metal oxides (TMOs) are considered as promising anode materials for lithium-ion batteries in comparison with conventional graphite anode. However, TMO anodes suffer severe volume expansion during charge/discharge process. In this respect, a porous Fe2O3 nanorod-decorated hollow carbon nanofiber (HNF) anode is designed via a combined electrospinning and hydrothermal method followed by proper annealing. FeOOH/PAN was prepared as precursors and sacrificial templates, and porous hollow Fe2O3@carbon nanofiber (HNF-450) composite is formed at 450 °C in air. As anode materials for lithium-ion batteries, HNF-450 exhibits outstanding rate performance and cycling stability with a reversible discharge capacity of 1398 mAh g−1 after 100 cycles at a current density of 100 mA g−1. Specific capacities 1682, 1515, 1293, 987, and 687 mAh g−1 of HNF-450 are achieved at multiple current densities of 200, 300, 500, 1000, and 2000 mA g−1, respectively. When coupled with commercial LiCoO2 cathode, the full cell delivered an outstanding initial charge/discharge capacity of 614/437 mAh g−1 and stability at different current densities. The improved electrochemical performance is mainly attributed to the free space provided by the unique porous hollow structure, which effectively alleviates the volume expansion and facilitates the exposure of more active sites during the lithiation/delithiation process.Graphical abstractPorous Fe2O3 nanorod-decorated hollow carbon nanofibers exhibit outstanding rate performance and cycling stability with a high reversible discharge capacity.