Lab-scale investigations on the processing of small powder volumes are of special importance for applications in additive manufacturing (AM) techniques. Due to the technological importance of high-silicon electrical steel, and the increasing need for optimal near-net-shape AM processing, the aim of this study was to investigate the thermal behavior of a high-alloy Fe-Si powder for AM. An Fe-6.5wt%Si spherical powder was characterized using chemical, metallographic, and thermal analyses. Before thermal processing, the surface oxidation of the as-received powder particles was observed by metallography and confirmed by microanalysis (FE-SEM/EDS). The melting, as well as the solidification behavior of the powder, was evaluated using differential scanning calorimetry (DSC). Due to the remelting of the powder, a significant loss of silicon occurred. The morphology and microstructure analyses of the solidified Fe-6.5wt%Si revealed the formation of needle-shaped eutectics in a ferrite matrix. The presence of a high-temperature phase of silica was confirmed by the Scheil–Gulliver solidification model for the ternary model Fe-6.5wt%Si-1.0wt%O alloy. In contrast, for the binary model Fe-6.5wt%Si alloy, thermodynamic calculations predict the solidification exclusively with the precipitation of b.c.c. ferrite. The presence of high-temperature eutectics of silica in the microstructure is a significant weakness for the efficiency of the magnetization processes of soft magnetic materials from the Fe-Si alloy system.