Novel hierarchical nanostructures composed of carbon coated α-Fe₂O₃ hollow nanohorns on carbon nanotube (CNT) backbones have been constructed by direct growth and thermal transformation of β-FeOOH nanospindles on CNTs, followed by carbon nanocoating. When evaluated as a potential anode material for lithium-ion batteries, such hierarchical structures exhibit superior lithium storage capabilities by virtue of their advantageous structural features.