By means of a specially designed multi-step synthesis procedure involving steps of precipitation, controlled oxidation, selective etching and calcination, porous double-shelled Mn2O3 hollow microspheres are synthesized. Solid, hollow and yolk-structured Mn2O3 are also similarly synthesized for comparison. X-ray diffraction, scanning and transmission electron microscopies, IR spectroscopy, thermogravimetry, and Brunauer-Emmett-Teller measurements are employed to investigate their structures and compositions. Galvanostatic cell cycling and impedance spectroscopy are used to characterize the electrochemical properties of Mn2O3/Li cells. The results show that the hierarchical hollow structured (double-shelled, hollow and yolk-structured) Mn2O3 anode materials deliver higher reversible capacities and excellent cycling stabilities than the solid Mn2O3. Moreover, among the three hierarchical hollow structured samples, the double shelled sample possesses the best cycling performance, especially at a high current density.