Ultrafine Fe2O3 nanorods anchored on graphene oxide (GO) are synthesized by a one-pot route under mild conditions in presence of KMnO4 and Ni foam. Ni foam is beneficial for the formation of Fe2O3 rather than FeOOH under otherwise the same conditions, while KMnO4 accelerates the hydrolysis of FeCl3, which promotes the nucleation of Fe2O3 and the achievement of uniform ultra-small morphology thereby. As an anode material for lithium-ion batteries, the Fe2O3/GO manifests a reversible capacity of 1004 mA h g−1after 500 cycles at 200 mA g−1, and even presents a high reversible capacity of 722 mA h g−1 at 1600 mA g−1. The excellent electrochemical properties of Fe2O3/GO are attributed to the ultrafine nanorods of Fe2O3 and the strong interaction between Fe2O3 and GO, which can reduce the diffusion distance of Li+ ions, enlarge the electrode/electrolyte contact area and improve the cyclic stability of iron oxide.