To achieve high-efficiency lithium ion batteries (LIBs), an effective active electrode material is vital. For the first time, mesoporous single crystals cobalt-doped Fe2O3 (MSCs Co-Fe2O3) is synthesized using formamide as a pore forming agent, through a solvothermal process followed by calcination. Compared with mesoporous single crystals Fe2O3 (MSCs Fe2O3) and cobalt-doped Fe2O3 (Co-Fe2O3), MSCs Co-Fe2O3 exhibits a significantly improved electrochemical performance with high reversible capacity, excellent rate capability, and cycling life as anode materials for LIBs. The superior performance of MSCs Co-Fe2O3 can be ascribed to the combined structure characteristics, including Co-doping and mesoporous single-crystals structure, which endow Fe2O3 with rapid Li+ diffusion rate and tolerance for volume change.