Eu2+/Ce3+ single doped and co-doped oxide glasses with high Gd2O3 concentration were prepared in a reducing atmosphere using a high-temperature glass melting method. Excitation and emission spectra measurements indicated that Ce3+ can enhance the luminescence intensity of Eu2+ effectively, which exhibited a 2.3 times increasa. The difference between the luminescence lifetimes of Eu2+ with and without Ce3+ doping indicated that the energy transfer efficiency could reach 61.5%, for which the energy transfer mechanism was investigated further. These researches suggest that co-doping method can significantly improve the luminescence capabilities of Eu3+ in the oxide glasses with high Gd2O3 concentration.