An electronic structure of Gd2(MoO4)3 was studied using methods of luminescence and X-ray photoelectron spectroscopy. Luminescent properties under excitation were investigated in energy ranges 125–165 and 526–553 eV which correspond to Gd4d and O1s shells. Luminescence excitation spectra were antibate to X-ray absorption spectra. The X-ray photoelectron spectroscopy appended these data by density of states in energy ranges where no resonant structures in excitation spectra were found. A low-temperature emission of Gd3+ ions was registered in gadolinium molybdate for the first time. Possible models of energy transfer in cation sublattice are discussed.