Hollow-structured hematite particles (HSHPs) with porosity in the nanometer size range have been successfully prepared using a one-step solvothermal process. A detailed time course study revealed that these HSHPs formed through a coupled dissolution and surface recrystallization process, in which the preformed hematite nanoparticles firstly oriented-aggregated into spindle-like particles with amorphous cores, then recrystallization occurred on the surfaces of the particles and was supplied by dissolution of the amorphous cores, which led to the final HSHPs. The as-prepared HSHPs performed remarkable catalytic activity in the polymerization reaction of benzyl chloride. These HSHPs might not only lead to novel technological applications in areas ranging from medicine to materials science, but also would shed more light on the attachment growth process of inorganic nanostructures with hollow interiors.