Hollow-structured α-Fe₂O₃ nanofibers were successfully synthesized by a simple electrospinning technique using iron acetylacetonate (Fe(acac₃)) and polyvinylpyrrolidone (PVP) precursor. Fe (acac)₃–PVP composite fibers were calcined at high temperature to form an interconnected 1D hollow-structure of α-Fe₂O₃ nanofibers. Thermogravimetric analysis (TGA), X-ray diffraction (XRD), field-emission scanning electron microscopy (FESEM), transmission electron microscopy (TEM) and Brunauer–Emmett–Teller (BET) were employed to characterize α-Fe₂O₃ hollow fibers. Based on the characterization results, a formation mechanism for electrospun α-Fe₂O₃ hollow fibers is proposed. Electrochemical measurements showed that the hollow-structure of α-Fe₂O₃ nanofibers played an important role in improving the electrode cycle stability and rate capability in lithium ion batteries. The α-Fe₂O₃ hollow fiber anodes exhibit a high reversible capacity of 1293 mA h g⁻¹ at a current density of 60 mA g⁻¹ (0.06 C) with excellent cycle stability and rate capability. Based on our study this high performance is attributed to the interconnected hollow-structure of large aspect ratio α-Fe₂O₃ nanofibers, which makes them a potential candidate for lithium ion batteries.