Ni3Sn4 and CoSn2 which are two Sn-based intermetallic compounds with different crystal structures have been tested as future negative electrodes for lithium-ion batteries. Various two-step reactions occur during the first discharge of these two electrodes. The first discharge shows good specific capacities: 515mAhg−1 for the Ni3Sn4 electrode and 606mAhg−1 for the CoSn2 electrode. These reactions lead to the formation of Li7Sn2, a Li-rich Li x Sn alloy characterized by 119Sn Mössbauer spectroscopy.