BaLiF3:Eu2+ was prepared by high temperature solid state reaction. The peaks of photoluminescence spectrum and photostimulated luminescence (PSL) spectrum are both at 410 nm which are attributed to the 5d-4f emission of Eu2+. The photostimulated luminescence excitation spectrum has its maximum at about 660 nm. Therefore, He-Ne laser is suitable for the reading-out process. The mechanism of PSL was also studied according to the characters of the spectra in the present paper. The PSL decay property of the glass ceramics was investigated, and it was shown that the storage information is easy to be erased. BaLiF3:Eu2+ has good properties of PSL and a promising future.