New blue luminescence glass-ceramic samples were prepared in air by annealing of the Eu3+-doped Li2O-BaO-B2O3 glass. The as-made glass samples only showed the sharp emission peaks assigned to the transitions of 5D0-7FJ (J=0, 1, 2, 3, 4) of Eu3+ ions. The glass-ceramic samples gave a strong and broad emission band peaking at about 382 nm ascribed to the 5d-4f transition of Eu2+ ions. The optical properties such as excitation and emission spectra, and the decay time of the Eu2+ ions were investigated in the glasses or the glass-ceramics samples. The X-ray diffraction pattern showed that LiBaB9O15 might be demonstrated to be the crystallites in the glass-ceramic, which contributed to the blue luminescence. SEM micrograph was investigated on the glass-ceramic samples obtained by crystallization of the glass matrix resulting in a mixture of poly-crystals.