The long, and short range order of the Li3(SbxBi1-x) alloys were studied using X-ray diffraction and NMR spectroscopy, respectively. For x = 0.25, the fcc unit cell volume determined by XRD showed a positive deviation from Vegard s la , indica i e of a endenc o ards phase segregation even though only a single crystalline phase could be determined. For x = 0.50, the asmilled material consisted of two fcc phases and subsequent annealing treatment decreased the relative quantity of the Bi-enriched phase as observed by XRD. NMR spectroscopy supported formation of Sb-rich clusters in these ternary alloys. The low activation energies determined by nuclear spin relaxation measurements suggest that these alloys would have a high rate capability when used as a Li-ion battery anode, in particular Li3Bi. When a 2:1 Li:Sb mixture was milled, Li3Sb and Sb metal were observed to form instead of the Li2Sb compound. This result shows that direct contact between SbxBi1-x and Li metal during milling is equivalent to setting an electrochemical half-cell to 0 V, thus leading to immediate formation of the phase with the highest Li content. This reaction mechanism is quite different from what would be expected under the operating conditions in a battery. Therefore, in-situ diffraction experiments on these binary SbxBi1-x solid solutions, both under constant current and constant potential conditions, would be an interesting direction for future research.