Aberration correction in the scanning transmission electron microscope combined with electron energy loss spectroscopy allows simultaneous mapping of the structure, the chemistry and even the electronic properties of materials in one single experiment with spatial resolutions of the order of one Ångström. Here the authors will apply these techniques to the characterization of epitaxial Fe/MgO/(001)Ge and interfaces with possible applications for tunneling junctions, and the authors will show that epitaxial MgO films can be grown on a (001)Ge substrates by molecular beam epitaxy and how it is possible to map the chemistry of interfaces with atomic resolution.