Large-scale Mn2O3 homogeneous core/hollow-shell structures with cube-shaped and dumbbell-shaped morphologies have been synthesized trough a facile and low-cost method. The microscopy analyses indicate that the core-shell microcubes have an average edge length of 2.5 渭m with a shell thickness of about 150 nm, and the core-shell microdumbbells were formed with a length of about 3 渭m and shell thickness of about 160 nm. The possible formation mechanism was discussed on the basis of transmission electron microscopy observations. The novel homogeneous core/hollow-shell structures were found to exhibit excellent performance in wastewater treatment.