The current study shows that there is a preferred orientation relationship between Ag3Sn and Ag in reaction between molten Sn and Ag. Due to the preferred orientation relationship, the morphology of Ag3Sn grains formed on (001) Ag single crystal is different from those formed on (011), (358) single crystal Ag, and polycrystalline Ag Facet scallop-type Ag3Sn grains formed irregularly on (011), (358) single crystal Ag, and polycrystalline Ag; whereas the regular Ag3Sn grains with parallel edges grew on (001) Ag single crystal, and they were elongated along two perpendicular directions. The orientation relationship between Ag3Sn grains and (001) Ag single crystal was determined using electron backscattered diffraction. The preferential growth of regular Ag3Sn grains with parallel edges formed on (001) Ag single crystal can be attributed to their minimum misfit.