Mn-90.8 wt%Sb alloys were solidified without and with high magnetic fields to investigate the effects of high magnetic fields on the structure evolution of the alloys. It was found that there were only MnSb/Sb eutectics without any primary phase in the alloy at 0 T, whereas a small amount of primary MnSb dendrites appeared in the MnSb/Sb eutectic matrix when the magnetic flux density was 4.4 T. In magnetic fields of 6.6, 8.8, and 11.5 T, both of two primary phases, i.e., MnSb and Sb, occurred in the matrix. In addition, the volume fraction of these two primary phases increased with increasing magnetic flux density. In magnetic fields of 8.8 and 11.5 T, primary MnSb dendrites aligned parallel to the magnetic field direction and gathered at the edge of the specimens. In contrast, primary Sb dendrites gathered in the center region of the specimens.