Hollow Mn2O3 core-shell microspheres were successfully fabricated via a mixed method including a solution method and a subsequent thermal decomposition. Transmission electron microscopy showed that the average size of Mn2O3 cores was about 0.8 μm and their shell thickness was 120 nm. These hollow Mn2O3 core-shell microspheres as anode materials exhibited a high specific capacity of up to 620 mA h g(-1) with a good cycling performance (500 cycles), indicating that the hollow Mn2O3 core-shell microsphere material was a promising anode candidate for a high-capacity, low-cost, and environment-friendly lithium ion battery. The formation mechanism was studied in detail.