Multi-shell hollow structure metal oxide materials, with the larger surface area and short diffusion lengths, are very promising for lithium-ion battery application as anode materials. However, the production of multi-shelled hollow structure is relatively cumbersome, and it is difficult to fabricate multi component metal oxide hollow structures. Herein, we developed a new one-step hydrothermal method for synthesizing α-Fe2O3 triple-shell hollow microspheres (TSHMs) by introducing urea as a coordination competitive agent. The triple-shell hollow structured α-Fe2O3 accommodates large volume change and provides abundant active sites enable it as an ideal material for lithium ion battery applications. We have demonstrated the high specific capacity of 903.6 mA h g−1 at a current density of 500 mA g−1 even after 1000 cycles by using the α-Fe2O3 TSHMs as anode material.