Pb-free solders based on near-eutectic Sn-0.7Cu-xNi alloys provide excellent solderability during wave soldering with cost advantages compared to Ag-containing alternatives. However, there is only limited knowledge of the solidification mechanisms in this alloy system and, furthermore, the ternary Sn-Cu-Ni phase diagram is not yet fully established. In this study, unidirectional solidification has been conducted in a Bridgman furnace using both binary alloys from the Sn-Cu6Sn5 system and ternary Sn-rich Sn-Cu-Ni alloys. The influence of Ni additions on the solidification mechanisms is assessed by comparing the microstructures of the ternary and binary alloys. The results are used to discuss the contrasting Sn-Cu-Ni phase diagrams reported in the literature. The results demonstrate the complex phase relations in the Sn-Cu alloy system, and the important role of trace amounts of various solute elements.