The electronic structure of the materials being measured has a strong effect on the spectroscopy of the interface between them measured by ballistic electron emission microscopy (BEEM). Specific calculations for CoSi2/Si(111) and NiSi2/Si(111) based on the calculated band structures of the materials illustrate some of the observable effects due to band structures, particularly of the overlayer. The BEEM spectra for CoSi2/Si(111) show a delayed onset due to a mismatch of the states near the conduction band minimum in the Si. The spectra for NiSi2/Si(111) show structure due to a decrease in the density of states in the NiSi2at ∼1.8 eV above the Fermi level.