Complex spinel Li2MnTi3O8 is prepared by a simple solid state reaction route. Electrochemical test shows that Li2MnTi3O8 reveals excellent electrochemical property as anode material with a reversible capacity of 193.8 mAh g(-1) and corresponding capacity retention of 88.0% after 50 cycles. In-situ X-ray diffraction observation reveals that Li2MnTi3O8 shows a quasi-reversible structural evolution during charge discharge process. For the lithium storage process, lithium-ion initially migrates to 4a position and forms Li-O octahedron at high lithiation potential, and then lithium-ion accommodates 8c position to form Li-O tetrahedron at low lithiation potential. The reverse charge process is quasi-reversible. As a result, Li2MnTi3O8 shows high structural stability as a promising lithium storage material for lithium-ion batteries. (C) 2014 Elsevier B.V. All rights reserved.