X-ray photoelectron spectroscopy was used to study the chemical composition and electronic structure of the Y 3 Al 5 O 12 :Yb (YAG:Yb) crystals. The contamination of the crystal with carbon and oxygen in the broken under UHV sample was found. The dopant concentration of Yb, in the mixed valence state, was determined as 12 %. The aluminium concentration is lower than a nominal value. The chemical shift analysis shows more ionic bond of Y-O than Al-O.