Tin/copper (Sn/Cu) coatings on Cu leadframes (CUFE), in which Fe atoms are doped as a minor element, showed whisker initiation at room temperature over a long period of 47 months. By means of the planar slice method and electron back scattering pattern (EBSP) measurement, the whisker roots were consistently found to be located at the intersections of grain boundaries in the coating. Whisker roots were also located above the peaks and ridge lines of intermetallic compound (IMC) Cu6Sn5, which was formed with a pyramid-shaped configuration between the Sn/Cu coating and Cu leadframe. Using finite element analysis (FEA), we calculated stress distribution in the coating. The results indicated that compressive stress normal to the grain boundary was induced with a gradient toward the surface in the coating. Therefore, the compressive stress gradient induced by the pyramid-shaped IMC is thought to be the root cause of whisker initiation in Sn/Cu coatings on Cu leadframes. When the Cu leadframe with a minor doped element of Cr atoms (CUCR) was used as the substrate with the same Sn/Cu coating, no whisker initiation was observed even after a longer storage time of 65 months. Through field-emission scanning transmission electron microscopy (FE-STEM) and field-emission transmission electron microscopy (FE-TEM) microstructural observations of vertical sections of each sample, the shape of the IMCs formed between the coating and the leadframe in the Sn/Cu-CUFE sample was found to be different from that in the Sn/Cu-CUCR sample. The difference in whisker initiation tendency can therefore be explained by the difference in compressive stress depending on the shape of the Cu-Sn IMCs, because stress distribution in the coating of the Sn/Cu-CUCR sample calculated using FEA revealed a smaller stress gradient than that in the Sn/Cu-CUFE sample.