Europium- and bromine-doped fluorozirconate glass-ceramics show a significant photostimulated luminescence (PSL) effect after X-irradiation at room temperature. The PSL is assigned to the 5 d -4 f emission of Eu 2+ ions incorporated in barium bromide crystallites which are formed in the glass matrix upon suitable thermal annealing. The BaBr 2 crystallites grows in both the hexagonal and orthorhombic phases. The PSL efficiency of the glass-ceramic containing predominantly the hexagonal phase is only about 0.0025% of the well-known crystalline storage phosphor BaFBr:Eu used as a standard, whereas the glass-ceramic containing the orthorhombic phase has a relative efficiency of a few percent. Using the same formulation for the fluorozirconate glass-ceramic, but replacing Na by Rb and Li, results in the formation of RbBa 2 Br 5 microcrystallites after suitable annealing. The relative PSL efficiency increases to about 10%. The structural changes in these two fluorozirconate glass-ceramics were monitored by X-ray diffraction, photoluminescence, and electron paramagnetic resonance.