Novel Eu3+-doped transparent oxyfluoride glass-ceramics containing BaLuF5 nanocrystals were successfully fabricated by melt-quenching technique for the first time. Analyses of XRD patterns prove that the new precipitated glass-ceramics are crystallized in cubic BaLuF5 based on isostructural BaGdF5. Intense red emissions observed in glass ceramics are attributed to the enrichment of Eu3+ ions into BaLuF5 nanocrystals. Besides, obvious stark splitting emissions, low forced electric dipole 5D0→7F2 transition, and long decay lifetimes of Eu3+ ions also evidence the partition of Eu3+ ions into BaLuF5 nanocrystals with low phonon energy. Such transparent material may find applications in photonics.