Fe₂O₃ nanorod/carbon nanofiber (CNF) composites were prepared by the electrochemical deposition of Fe₂O₃ on a web of CNFs, which was then used as a free-standing anode. The conductive, three-dimensional structure of the CNF web allowed for the electrodeposition of the Fe₂O₃ nanorods, while its high conductivity made it possible to use the composite as a free-standing electrode in lithium-ion batteries. A free-standing electrode, which does not use polyber binder, substrate, and conductive additive, prevented a recution of rate-capability owing to the non-conductive polymer binder. In addition, it was easy and cheap to fabricate by a simplification of a process of cell preparation. The nanorod-like Fe₂O₃ structures could only be electrodeposited on the CNFs; flake-like Fe₂O₃ was formed on flat conductive glass substrates. It can be attributed to the different growth mechanism of Fe₂O₃ on the CNFs because of the large number of reaction sites on the CNFs, differences in the precursor concentration and diffusivity within the CNF web. The formation of aggregates of the Fe₂O₃ particles on thicker CNFs also indicated that the CNFs had determined the Fe₂O₃ growth mechanism. The synthesised Fe₂O₃/CNF composite electrode exhibited stable rate capacities at different current densities. This suggested that CNF-based composite did not exhibit the intrinsic disadvantages of Fe₂O₃. Finally, carbon coatings were deposited on the Fe₂O₃/CNF composites to further improve their electronic conductivity and rate capability. The strategy adopted in this study of using a web of CNFs as the substrate for the electrodeposition of Fe₂O₃ and of using the resulting composite material as a free-standing electrode  or LIBs should also be applicable in the case of other metal oxide/CNF composites.