Alkaline earth borate glasses are being studied due to their interesting structure and properties. Here, the optical properties of some barium oxyfluoride glasses are reported. The absorption spectra by means of Judd Ofelt theory, the room temperature luminescence, and the thermoluminescence (TL) response as a function of dopant concentration were studied. The effect of the concentration on the thermal stability and the glass structure was also analyzed. The incorporation of Nd 3+ affects not only the optical properties but also the thermal ones. From Raman spectroscopy, no great differences were observed among undoped and doped glass samples. Judd-Ofelt parameters are lower or comparable to other borate and silicate systems. The temperature of the maximum intensity on the TL curve does not change with the irradiation dose, indicating samples follow a first-order kinetic model. However, the detailed TL analyses evidenced a continuous distribution of the activation energy and the signal stability after irradiation was also studied and interpreted in the same way. The results presented here indicate that the oxy-fluoride borate glasses are promising materials for TL applications.