A Cu6Sn5 layer is an integral part of many electronic interconnections. Here we show that, although primary Cu6Sn5 is not a potent nucleant for Sn, the Cu6Sn5 layer plays a key role in Sn nucleation and microstructure formation in solder joints. Combining thermal analysis, FIB-tomography and EBSD, we show that conical cavities are present between the scallops of the Cu6Sn5 layer that act as geometric nucleation sites for Sn, that Sn grows from the Cu6Sn5 layer, and that reproducible nucleation orientation relationships (ORs) exist between Cu6Sn5 and Sn. With these ORs, a near-random distribution of Sn orientations is predicted from joint to joint even for Cu6Sn5 layers with a strong [0001] fibre texture. It is shown that the nucleation undercooling is strongly affected by manipulation of the Cu6Sn5 layer shape, and that it is possible to prevent nucleation on the Cu6Sn5 layer by adding more potent nucleants.