Oxyfluoride borosilicate glass with the molar composition of 60SiO 2 -15B 2 O 3 -15Na 2 O-8CaF 2 -2NaF-0.25Eu 2 O 3 was synthesized by a traditional glass melting method. Glass ceramics containing CaF 2 nanocrystals were prepared by heat treating the glass samples at a temperature in the range of 620–680 °C. The results of X-ray diffraction (XRD) indicated that the average crystallite size and the lattice constant of CaF 2 nanocrystals increased with the heat treatment temperature increasing. The luminescence spectra showed that the emission intensity of Eu 3+ doped glass ceramics was stronger than that of the glass matrix, and increased with the heat treatment temperature increasing. The left edge of excitation band shifted to shorter wavelength in the glass ceramics. The local environments of Eu 3+ ions in the glass and glass ceramics were different.