Uniform crystalline MgSn(OH)6 nanocubes were synthesized by a hydrothermal method. The influences of reaction conditions were investigated and the results showed that the solvent constituents significantly affected the shape and size of MgSn(OH)6·SnO2/Mg2SnO4 has been obtained by thermal treatment at 850°C for 8h under a nitrogen atmosphere using MgSn(OH)6 as the precursor. The electrochemical tests of SnO2/Mg2SnO4 revealed that SnO2/Mg2SnO4 has a higher capacity and better cyclability compared to pure SnO2 or Mg2SnO4. The electrochemical performance of SnO2/Mg2SnO4 was sensitive to the size of the nanoparticles. The lithium-driven structural and morphological changes of the electrode after cycling were also studied by the ex-situ XRD pattern and TEM tests. This work indicates that SnO2/Mg2SnO4 is a promising anode material candidate for application in Li-ion batteries.