We present a detailed structural characterization of the interfaces in Fe/MgO/Fe layers grown by molecularbeam epitaxy using aberration-corrected transmission electron microscopy ͑TEM͒, scanning TEM, and electron energy-loss spectroscopy. When fabricated into magnetic tunnel junctions, these epitaxial devices exhibit large tunnel magnetoresistance ratios ͑e.g., 318% at 10 K͒, though still considerably lower than the values predicted theoretically. The reason for this discrepancy is being debated and has been attributed to the structure of, and defects at the interface, namely, the relative position of the atoms, interface oxidation, strain, and structural asymmetry of the interfaces. In this structural study, we observed that Fe is bound to O at the interfaces. The interfaces are semicoherent and mostly sharp with a minor degree of oxidation. A comparison of the two interfaces shows that the top MgO/Fe interface is rougher.