The biomedical industry has an increasing demand for processes to join dissimilar metals, such as laser welding of NiTi and stainless steel wires. A region of the weld close to the NiTi interface, which previously was shown to be prone to cracking, was further analyzed by energy dispersive spectrometry (EDS) extended in the third dimension using a focused ion beam. As the spatial resolution of EDS analysis is not precise enough to resolve the finest parts of the microstructure, a new segmentation method that uses in addition secondary-electron images of higher spatial resolution was developed. Applying these tools, it is shown that this region of the weld close to the NiTi interface does not comprise a homogeneous intermetallic layer, but is rather constituted by a succession of different intermetallics, the composition of which can be directly correlated with the solidification path in the ternary Fe-Ni-Ti Gibbs simplex.