We report on the growth of epitaxial Fe/MgO/Ge(001) heterostructures by molecular beam epitaxy. The lowest oxidation and highest sharpness of the MgO/Ge interface, corresponding to a transition layer on the order of one Ge unit cell, is obtained for room temperature growth of the MgO layer followed by annealing in a vacuum at 500 °C. In these conditions, the MgO layer grows epitaxially on Ge(001) with the [110] direction parallel to the [100] direction of Ge, at variance with the cube-on-cube growth on Si(001) and GaAs(001). However, in some cases, the cube-on-cube growth mode of MgO on Ge competes with the mode involving a 45° rotation, as revealed by transmission electron microscopy and photoelectron diffraction data on MgO films grown at 300 °C without postannealing, and on p-doped Ge substrates. For the Fe overlayer, in all the cases reported, room temperature growth followed by annealing up …