Sn-rich La–Co–Sn ternary alloys were obtained by arc-melting process and subsequent ball-milling. X-ray diffraction (XRD) and scanning electron microscopy (SEM) were used to determine the structure and morphology of the obtained alloys. In addition, the galvanoststic discharge/charge test, cyclic voltammetry (CV) and electrochemical impedance spectroscopy (EIS) were carried out to characterize the electrochemical properties of these alloys as anode materials for Li-ion batteries. It is found that all the as-cast La–Co–Sn ternary alloys have the same main phase of La3Co4Sn13 and low electrochemical capacities. Among these alloys, the as-cast LaCoSn4 alloy exhibits the best electrochemical performance. The ball-milling process results in the reduced cystallinity, and the enhanced electrochemical capacities as compared to the as-cast alloy. In particular, the LaCoSn4 alloy, obtained after ball-milling for 16h, provides the higher reversible discharge capacity and the better cycle stability.