The powder α-Eu2(MoO4)3 sample was prepared by the solid-state reaction method. The phase purity of the final powder product was verified by X-ray diffraction analysis. The constituent element core levels and valence band are measured by X-ray photoelectron spectroscopy as a function of Ar+ ion (2.5 keV, 7–8 μA/cm2) bombardment time. The formation of Mo5+ and Mo4+states at high bombardment times was detected. The Eu–O and Mo–O bonding was considered in comparison with other Eu3+- and Mo6+-containing oxides using binding energy difference parameters.