X-ray photoelectron spectroscopy (XPS/ESCA) has been employed to investigate pure single crystals and powdered samples of yttrium aluminum garnet, Y3Al5O12 (YAG), and YAG crystals doped with several rare earth elements (Ln = Pr, Er, Ho, Tm) and a transition metal (Cr). Core level XPS peak shapes of the main elements forming the garnet structure can be rationalized due to different structural environments of particular ions modified by doping. The change of dopant oxidation state also results in variation of XPS peaks and helps to identify the sites in which it takes place. Single-crystal and powder samples give different XPS spectra. Possible sources of these differences are discussed. Similarities and differences between simple and mixed oxides are shown. The structure of YAG suggests the presence of only one independent oxygen ion; however the O(ls) spectra of all YAG systems exhibit two readily discerned peaks, An explanation for this dichotomy is discussed, involving the possible polarization of the oxygen valence electron density between the aluminum and yttrium, Alternative explanations are also considered.