With the development of large-scale energy storage, sodium-ion batteries gradually get more attention. Iron oxide is cheap, non-toxic and its high theoretical capacity makes it promising as the dominant anode material for commercial scale sodium storage. A simple hydrothermal method and carbon-template method for preparing porous α-Fe₂O₃ nanospheres were employed. The nano-material shows high-rate capability and long-term cyclability when applied as an anode material for Na-ion batteries (SIBs). As a result, porous α-Fe₂O₃ nanospheres show an initial discharge specific capacity of up to 520 mAh/g at a current density of 50 mA/g. Due to the simple synthesis technique and high electrochemical performance, porous α-Fe₂O₃ nanospheres have a great potential as anode materials for rechargeable SIBs. The unique structure of the porous α-Fe₂O₃ nanospheres offers a synergistic effect to alleviate stress, accommodate large volume change and facilitate the transfer of electrons and electrolyte during prolonged cycling.