The electrochemical performance of a material varies with its structural phase transition. It is found that the rhombohedral Fe2O3 can transform to the cubic Fe3O4 via a calcination treatment in a nitrogen atmosphere, and lithium-ion storage performances of Fe3O4 get an obvious improvement due to its structural advantages. On the basis of data calculated by X-ray diffraction, the larger unit cell volume as well as the higher void fraction of cubic Fe3O4 provides lithium-ions with more transport channels for Li ions diffusion and storage without serious volume change, and thus the cubic Fe3O4 delivers an excellent reversible capacity of 921.1mAhg−1 after 15 cycles at the current density of 50mAg−1, which is much higher than 328.3mAhg−1 for the rhombohedral Fe2O3. To further enhance the structural stability of electrodes, reduced graphene oxide is introduced. The Fe3O4/reduced graphene oxide show an excellent specific capacity of 825.3mAhg−1 after 40 cycles and impressive rate performance of 600mAhg−1 at the current density of 400mAg−1, which are much higher than that of Fe3O4 (417 and 300mAhg−1), Fe2O3 (137.4 and 95mAhg−1) and Fe2O3/reduced graphene oxide (390.1 and 480mAhg−1). These results demonstrate that the structural phase transition and reduced graphene oxide of Fe3O4/reduced graphene oxide composites offer unique characteristics suitable for high-performance energy storage application.