New oxyfluoride glasses of 1Eu2O3–50BaF2–xAl2O3–(50−x)B2O3 (x=0–25), yEu2O3–50BaF2–25Al2O3–25B2O3 (y=0–10) (mol), and zEu2O3–1Tb4O7–50BaF2–25Al2O3–25B2O3 (z=0, 0.5) (mol) with a high fluorine content (F/(F+O)=0.4) were synthesized by using a conventional melt-quenching method, and photoluminescence properties such as quantum yield (η), lifetime (τ), and concentration quenching effect of Eu3+ ions were clarified. The glass with 25Al2O3 showed an excellent red luminescence with extremely high quantum yield (η) of 97% in the visible region at the excitation of the wavelength λ=396nm and a long lifetime of τ=3.29ms for the emission (λ=612nm) of Eu3+ ions at the 5D0 level. The effect of concentration quenching in these glasses was also very small, e.g., η=72% even for the glass with 10Eu2O3. The values of η=52% for the green emission of Tb3+ ions and of η=81% for the yellow emission of Eu3+–Tb3+ co-doped ions were also achieved in the glasses. The present study indicates that rare-earth ions of Eu3+ and Tb3+ are dispersed homogeneously in these oxyfluriode glasses and the degree of their its asymmetry (i.e., the electric field gradient) is also widely distributed due to the coordination of both F− and O2− ions. The new oxyfluoride glasses with high BaO and Al2O3 contents have a high potential as hosts for new phosphors with rare-earth ions.