An ab initio method with the first-principles plane-wave pseudopotentials based on the density functional theory has been used to calculate the physical character and electrochemical performance of various alloy phases in Li-Sn alloy. The results show that Li5Sn2 alloy phase, with relatively small volume expansion ratio and large reversible capacity, is an ideal alloy electrode phase. On the other hand, many kinds of tin thin film electrodes were fabricated by direct current and radio frequency magnetic sputtering on copper foil collector as anode materials for lithium-ion batteries. The values of calculated Li intercalated potential using the CASTEP program are well consistent with the experimental values.