The Eu2+-doped glass ceramics containing BaF2 nanocrystals were prepared and their luminescence properties were investigated. The excitation spectra of Eu2+-doped glass ceramics showed an excellent overlap with the main emission region of an ultraviolet light-emitting diode (UV-LED) centered at 380 nm. The 450 nm emission of Eu2+ in glass ceramics under the 385 nm excitation was much stronger than that in glass. The Eu2+-doped glass ceramics containing BaF2 nanocrystals may be used as a potential blue-emitting phosphor for UV-LED.