To achieve high-efficiency lithium ion batteries (LIBs), an effective active electrode material is vital. For the first time, mesoporous single crystals cobalt-doped FeO (MSCs Co-FeO) is synthesized using formamide as a pore forming agent, through a solvothermal process followed by calcination. Compared with mesoporous single crystals FeO (MSCs FeO) and cobalt-doped FeO (Co-FeO), MSCs Co-FeO 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-FeO can be ascribed to the combined structure characteristics, including Co-doping and mesoporous single-crystals structure, which endow FeO with rapid Li diffusion rate and tolerance for volume change.