The shell-ferromagnetic effect originates from the segregation process in off-stoichiometric Ni–Mn-based Heusler alloys. In this work, we investigate the precipitation process of L21-ordered Ni2MnSn and L10-ordered NiMn in off-stoichiometric Ni50Mn45Sn5during temper annealing, by X-ray diffraction (XRD) and119Sn Mössbauer spectroscopy. While XRD probes long-range ordering of the lattice structure, Mössbauer spectroscopy probes nearest–neighbour interactions, reflected in the induced Sn magnetic moment. As shown in this work, the induced magnetic Sn moment can be used as a detector for microscopic structural changes and is, therefore, a powerful tool for investigating the formation of nano-precipitates. Similar research can be performed in the future, for example, on different pinning type magnets like Sm-Co or Nd-Fe-B.