The Au N 67 VV Auger transition may take place after direct ionization of the N 67 subshells or after ionization of the N 45 subshells followed by the Coster–Kronig transitions N 45 N 67 V. The subshells N 67 and N 45 have much different ionization energies, by a factor of four, and this creates a problem in quantification of the N 67 VV signal. Calculations of the backscattering factor from the analytical expressions require knowledge of a single value of the ionization energy. Furthermore, a single value of the ionization energy is needed in calculations of the ionizations cross section. An attempt is made here to decide which ionization energy should be used in calculations by comparison of the experimental energy and emission angle dependence of the AES signal intensity with this dependence determined from theory using different ionization energies. It has been found that the N 67 VV signal intensity is strongly dominated by ionizations of the N 5 subshell. Furthermore, the ionization cross section for the N 5 subshell is well described by the Casnati et al. formula.