This article presents a method for determining the interfacial chemical composition of semiconductor thin films. Some of the materials and interfaces characterized by this technique are tungsten silicide, titanium nitride, silicon nitride, titanium silicide, and aluminum. These thin film materials are typically supported on conductive (silicon, polysilicon) and nonconductive (boron-doped phosphosilicate glass) substrates. The determination of their interfacial chemical compositions is enhanced by using the zirconium anode (2042.4 eV). The simultaneous use of magnesium and zirconium anodes allows the analysis of the photoelectrons as well as the corresponding higher energy Auger electrons for such materials as silicon and aluminum. The kinetic energies of the Al KLL and Si KLL are beyond the Fermi level (zero binding energy) of either the magnesium (1253.6 eV) or aluminum (1486.6 eV) anodes. The photoelectron used in conjunction with thin film Auger electrons provides the energy necessary for determining Auger parameters, which are independent of localized sample charging and provide their chemical identification. Charging is common to many of these materials and is especially prevalent when analyzed using an increasingly common monochromatized aluminum source for excitation Thus, the simultaneous use of the magnesium (1253.6 eV) and zirconium (2042.4 eV) anodes is charge independent and provides interfacial chemical identification.