Nanostructured electrodes have significant potential for enhancing the kinetics of lithium storage in secondary batteries. A simple and economical manufacturing approach of these electrodes is crucial to the development and application of the next generation lithium ion (Li-ion) batteries. In this study, nanostructured α-Fe2O3 electrode is fabricated by a novel one-step flame combustion synthesis method, namely Reactive Spray Deposition Technology (RSDT). This process possesses the merits of simplicity and low cost. The structure and morphology of the electrode are investigated with X-ray diffraction, scanning electron microscopy (SEM) and transmission electron microscopy (TEM). Electrochemical performance of the nanostructured α-Fe2O3 electrodes as the anodes for Li-ion batteries is evaluated by cyclic voltammetry, galvanostatic charge/discharge and electrochemical impedance spectroscopy in coin-type half-cells. The as-prepared electrodes demonstrate superior cyclic performance at high current rate, which delivers a high reversible capacity of 1239.2 mAh g−1 at 1 C after 500 cycles. In addition, a discharge capacity of 513.3 mAh g−1 can be achieved at 10 C.