Due to high theoretical specific capacity and low cost, Fe2O3 has become an attractive research field in anode materials for lithium-ion batteries (LIBs). In this study, by using PVP/FeCl3 solutions with different concentrations as precursors, Fe2O3 nanofibers with different diameters were prepared by electrospinning technology and anneal treatment. In addition, Fe2O3 nanoparticles were prepared by hydrothermal synthesis method. The crystalline structure, morphology and electrochemical performances of the composites were investigated by X-ray diffraction, thermogravimetric analysis, infrared spectrum, scanning electron microscope, transmission electron microscope, and charge-discharge tests. Results showed that Fe2O3 nanofibers has better electrochemical performance than Fe2O3 nanoparticles. Fe2O3 nanofibers with diameter of 160 nm exhibited the highest rate and cycle performance as anode material in LIBs. It was found that the Fe2O3 electrode could deliver a discharge capacity of 827.3 mAh/g at 0.1 A/g current density and 439.1 mAh/g at 2 A/g after 70 cycles.