alpha-Fe2O3 hollow spheres with sheet-like subunits are synthesized by a facile quasiemulsion-templated method. Glycerol is dispersed in water to form oil-in-water quasiemulsion microdroplets, which serve as soft templates for the deposition of the alpha-Fe2O3 shell. When tested as anode materials for lithium-ion batteries, these alpha-Fe2O3 hollow spheres manifest greatly enhanced Li storage properties.