When the surface of a solid sample is irradiated under vacuum by x-rays an electron emission, owing to photoabsorption, can be measured. As the electrons are detected under neglection of their kinetic energies the total electron yield (TEY) is determined. With a tuneable x-ray monochromator the TEY is measured below and above of one of the absorption edges of a given element. A jumplike increase of the TEY signal, due to the additional photoabsorptions in the corresponding atomic level, can be observed – qualitative analysis. The height of this jump can be correlateted to the concentration – quantitative analysis. It can be shown by a fundamental parameter approach for primary and secondary excitations how to use TEY for a quantitative analysis. The information depth λ of this new method is approximately 2–400 nm depending on the chemical elements and on the original kinetic energies of Auger and photoelectrons. Thus, TEY is located between photoelectron spectrometry and x-ray fluorescence analysis.