Gd/Tb、Gd/Ce、Gd/Ce/Tb doped SiO2-B2O3-BaF2 fluorine oxide glass was prepared by high temperature melting method. The phase of fluorine oxide glass was determined by X-ray diffraction spectrum. The luminescence properties of Tb3+ doped with different Gd2O3 content were studied by the fluorescence spectra of Tb3+ under different excitation bands, and the more accurate numerical range of optimal Gd2O3content was determined. Gd/Ce/Tb co-doped fluorine oxide glass was prepared by changing the atmosphere. The sensitization of Gd3+ and Ce3+ to Tb3+ was studied. The results show that the prepared fluorine oxide glass has a stable glassy state. Both Gd3+ and Ce3+sensitize the luminescence of Tb3+, and the sensitization effect is most significant when Gd2O3 content is 7% (molar fration， the same below) compared with other content, and quenching occurs when Gd2O3 content exceeds 7%. Cerium can coexist in Ce3+ and Ce4+ valence states in Ce2O3 doped glass, and it is easier to maintain Ce3+ state when doped in reducing atmosphere than in air atmosphere. Moreover, Ce3+ sensitizes the luminescence of Tb3+, while Ce4+ inhibites the luminescence of Tb3+.