Fe-bearing MgO [(Mg1−xFex)O] is considered a major constituent of terrestrial exoplanets. Crystallizing in the B1 structure in the Earth’s lower mantle, (Mg1−xFex)O undergoes a high-spin (S = 2) to low-spin (S = 0) transition at ∼45 GPa, accompanied by anomalous changes of this mineral’s physical properties, while the intermediate-spin (S = 1) state has not been observed. In this work, we investigate (Mg1−xFex)O (x ≤ 0.25) up to 1.8 TPa via first-principles calculations. Our calculations indicate that (Mg1−xFex)O undergoes a simultaneous structural and spin transition at ∼0.6 TPa, from the B1 phase low-spin state to the B2 phase intermediate-spin state, with Fe’s total electron spin S re-emerging from 0 to 1 at ultrahigh pressure. Upon further compression, an intermediate-to-low spin transition occurs in the B2 phase. Depending on the Fe concentration (x), metal–insulator transition and rhombohedral distortions can also occur in the B2 phase. These results suggest that Fe and spin transition may affect planetary interiors over a vast pressure range.