AbstractSpectra obtained by a new soft x-ray emission spectroscopy(SXES) apparatus again exhibited clear differences among Si-compounds and Si crystal. A non-destructive analysis of an annealed transition metal(TMSi:film)/Si(111) contact system was carried out using either the distinct differences of Si L2, 3 SXES spectra between TMSi's and Si single crystals or the fad that the soft x-ray production depth increases in a solid with the energy of the primary electron, Ep. It was shown that the apparatus was capable of exploring electronic and atomic structures of a multi-layered contact system grown on a Si(111) substrate.