Iron oxide film with spaced radial nanorods is formed on the VGCF (vapor-grown carbon nanofiber) scaffolds by means of anodic electrodeposition. X-ray diffraction, scanning electron microscopy, and transmission electron microscopy show that the iron oxide film deposited on the VGCF surface is α-Fe2O3 and consists of spaced radial nanorods having 16–21nm in diameter after annealing at 400°C. Galvanostatic charge/discharge results indicate that the α-Fe2O3/VGCF anode (970mAhg−1) has higher capacity than bare α-Fe2O3 anode (680mAhg−1) at 10C current discharge. VGCF scaffolds fabricated by electrophoretic deposition favor the electron conduction, and the spaced radial nanorods on VGCFs facilitate the migration of lithium ion from the electrolyte. Electrochemical reactions between α-Fe2O3 and lithium ion are therefore improved significantly by this tailored architecture.