Difficult nucleation of β-Sn during solidification of tin and tin-based lead-free solder alloys can result in high degrees of undercooling of the liquid prior to solidification. The undercooling can produce solder joints with large grains, anisotropic behavior, and undesirable mechanical properties. This paper describes our examination of the amount of undercooling of tin on both graphite (non-wetting) and copper (wetting) surfaces using in situ x-ray diffraction. The microstructure was further characterized by optical microscopy, scanning electron microscopy, and electron backscattering diffraction imaging microscopy. Undercoolings as high as 61°C were observed for Sn solidified on graphite, while lower undercoolings, up to 30°C, were observed for Sn solidified on copper. The microstructure of the high purity Sn sample solidified on graphite showed very few grains in the cross-section, while the commercially pure Sn sample solidified with only one grain and was twinned. Tin solidified on copper contained significant amounts of copper in the tin, intermetallic phase formation at the interface, and a eutectic microstructure.