The methodology of characterizing electronic structure in dielectric materials will be presented in detail. Energy distribution of the electrons emitted from dielectric materials by the Auger neutralization of ions is measured and rescaled for Auger self-convolution, which is restructured from the energy distribution of the emitted electrons. The Fourier transform is very effective for obtaining the density of states from the Auger self-convolution. The MgO layer is tested as an example of this new measurement scheme. The density of states in the valence band of the MgO layer is studied by measuring the energy distribution of the emitted electrons for MgO crystal with three different orientations of (111), (100) and (110). The characteristic energy of to corresponding to the peak density of the states in the band is determined, showing that the (111) orientation has a shallow characteristic energy epsilon(0) = 7.4 eV, whereas the (110) orientation has a deep characteristic energy epsilon(0) = 9.6 eV, consistent with the observed coefficient gamma of the secondary electron emission for MgO crystal. Electronic structure in new functional nano-films spayed over MgO layer is also characterized. It is therefore demonstrated that secondary electron emission by the Auger neutralization of ions is highly instrumental for the determination of the density of states in the valence band of dielectric materials. This method simultaneously determines the valence band structure and the coefficient T of the secondary electron emission, which plays the most important role in the electrical breakdown phenomena. (C) 2012 Elsevier B.V. All rights reserved.