Spinel Zn2SnO4 particles with the cubic shape are prepared via a hydrothermal reaction under mild conditions. The hydrothermal conditions, such as alkaline concentration, reaction temperature, and duration time, have an important influence on the product structure and the performance of the electrode prepared with the product. The optimized product is cube-shaped Zn2SnO4 crystalline, which is prepared with 0.4 M of NaOH solution at 200 degrees C for 24 h. These cube-shaped Zn2SnO4 particles with the spinel structure exhibit a large electrochemical capacity of 988 mA h/g and a relatively good capacity retention as anode materials for Li-ion battery. The structures of the as-prepared product and specimens taken from the electrodes after charging-discharging cycles are analyzed by X-ray diffraction, scanning electron microscopy, and transition electron microscopy techniques. In particular, it is found for the first time that the spinel Zn2SnO4 structure exists to a great extent after the first cycle and contributes to the extremely high reversible capacity during the following cycles.