We report the soldering behaviors of high-temperature (300 °C) lead-free SnSb alloys on Cu foils and phased-in Cu-Cr thin films. By increasing the Sb content from 5 to 15 wt%, the solder surface became rougher and the wetting angle decreased from 50° to 20° on the Cu foils. Interfacial compounds were found to be Cu6Sn5 and Cu3Sn. The Cu6Sn5 showed a scallop-type morphology, whereas the Cu3Sn had a layer-type morphology. The growth of the latter was found to be diffusion limited. On phased-in Cu-Cr thin films, the solders showed much lower wetting angles than on the Cu foils, but the dewetting phenomenon was observed after 1 min of reflow time in the 85Sn15Sb alloy. In comparison, we found no dewetting of the high-temperature 95Pb5Sn solder.