Principles and performances of Primary-beam Diffraction Modulated Electron Emission are briefly reviewed. This approach exploits the spatial modulation of the beam electrons waves intensity in ordered atomic arrays, which in turn results in a marked dependence of the electron emission on the incidence angle. Detection of Auger electrons or inelastically backscattered electrons (ionization losses) provides chemical specificity. Surface sensitivity is related to the inelastic mean free path of the detected electrons. Examples are given of the capability of this technique for structural characterization of buried layer and interfaces. They include: i) epitaxial growth of Co oxide on the (001) surface of Co bct film, ii) subsurface behaviour of Co epitaxial layers during the bct→hcp phase transition.