We prepared composite electrodes of iron silicide/Si by using mechanical grinding for mixtures of ferrosilicon and Si followed by gas-deposition, and investigated their electrochemical properties as Li-ion battery anode. With increasing the mechanical grinding time, the phase transformation from FeSi to FeSi2 took place more significantly, and the composite electrode showed better cycle stabilities. There was no remarkable difference in mechanical properties and electronic conductivity between FeSi and FeSi2. On the other hand, the FeSi2 electrode exhibited about three times larger capacities in comparison with the FeSi electrode. In addition, a result of our first principle calculation indicates that Li-ion can diffuse more easily in FeSi2 lattice than in FeSi lattice. It is suggested that the better cyclability of the composite electrodes was attributed to the moderate reactivity of FeSi2 with Li and the smooth Li-ion diffusion in it.