The capability of Auger transition probabilities experimentally derived from X-ray excited Auger electron spectra in XPS were tested. The relative sensitivity factor (RSF) method has been employed in the quantification by AES (Electron excited Auger electron spectroscopy). However, the difference between experimentally derived RSF and theoretically calculated ones has been found in some reports. One of the great reason of the difference may be caused by the calculated values of the Auger transition yield which has been commonly employed without the consideration of the allotment of coupling scheme in the transition selected in the quantification for instance, the allotment of each six coupling KL1L1, KL1L2, KL1L3, KL2L2, KL2L3, and KL3L3 in KLL transition. The employment of derived Anger transition probabilities reduce the difference between theoretically calculated RSF and experimentally derived one.