Nanostructures have received great attention to improve the performance of lithium-ion batteries, due to their advantages in dealing with critical issues associated with large volume change, low electrical conductivity, and slow rate of Li+ diffusion. To realize large lithium storage capacity and excellent rate capability of iron oxide electrode. Carbon-modified three-dimensional porous iron oxide was prepared by chemical reaction with in situ formation of templating agent followed by the calcination is reported herein. Benefit from the regulation of the number of pores in the precursor, part of Fe is oxidized to Fe3O4 and part of Fe is peroxidized to Fe2O3, thus forming Fe2O3/Fe3O4 heterostructure during oxidation process. Attributed to its unique structural feature, the 3D Fe2O3/Fe3O4-C heterostructure electrode for the anode of lithium-ion batteries exhibits outstanding rate capability, i.e., 911.4, 797.9, 736.3, 597.8, and 402.6 mAh g−1 at 0.3, 1.0, 2.0, 5.0, and 10.0 A g−1, respectively, and high reversible capacity, i.e., 929.1 mAh g−1 at a low current density of 300 mA g−1. © 2020, Springer-Verlag GmbH Germany, part of Springer Nature.