We report some of the results of extensive experimental and theoretical studies by our group of the XPS and Auger spectra of the transition and noble metals and some of their alloys: we concentrate on those aspects of the spectra which regard the determination of electronic structure. Consideration of the Auger kinetic energies yields insight into screening mechanisms and suggests methods for extracting electronic structure changes in alloys from XPS and XAES shifts. We demonstrate that the charge transfer in a number of alloys (AuPd, CuPd, AgPd, AuCu, AgAu and CuNi) appears to be negligible (i.e., on the order of hundredths of electrons/atom). Examples (i.e., AuZn, AuMg, AuPd, AgPd and CuNi) of the results for the d- and sp-electron occupations are given. (C) 2004 Elsevier B.V. All rights reserved.