The glass structure and photoluminescence of new oxyfluoride glasses with the composition of xMgF(2)-(66.7-2x/3)BaO-(33.3-x/3)B2O3 (x = 10-50 mol%) were investigated in this work. The structure of the glasses was investigated by magic-angle spinning NMR, XAS, and Raman scattering spectroscopies. It was revealed that the glasses are mainly composed of BO3 units with a disconnected borate network consisting mainly of ortho- and pyro-borate units, and ortho-borate increases with the addition of MgF2. The fluorine atoms are surrounded by Mg2+ and Ba2+ ions. The photoluminescence of Eu3+-doped samples were investigated. It was indicated that asymmetry of the Eu3+ site increased with the addition of MgF2. The photoluminescence quantum yield (eta) of the glasses are very high and increased with MgF2 addition; red photoluminescence is observed with eta = 82% for 10MgF(2) and eta = 98% for 50MgF(2) for excitation at 393 nm.