Sn-Bi nanometer powders were produced by an electrohydrodynamic technique. The microstructural feature of Sn-Bi nanometer powders was investigated by means of XRD, TEM and HREM. The results show that Sn-Bi nanometer powders produced are composed of tetragonal β-Sn monophase supersaturated solid solution and rhombohedral Bi monophase supersaturated solid solution. Most of the Sn-Bi nanometer powders are single crytals, only a few Sn-Bi nanometer powders are twin crystals. The particles of﹤10nm in diameter are perfect single crystals. There exist dislocations in the particles larger than 10nm in diameter. The formation mechanism of microstructure for Sn-Bi nanometer powders is analyzed.