We have examined the photoluminescence (PL) and X-ray luminescence (XL) of fluorochlorozirconate (FCZ) glass-ceramics (FCZ-GC) doped with Sm3+ and Sm2+ ions. Sm-doped FCZ-GCs have been prepared by annealing a ZBLAN glass of nominal composition 53% ZrF(4), 20% NaF, 3% AlF(3), 3% LaF(3), 1% SmF(3), 1% BaF(2), 19% BaCl(2) (mol%) above the glass transition of the host glass matrix. SmF(3) was added to the initial glass mix for trivalent samarium doping. Sm2+ doping was achieved by reducing Sm3+ to Sm2+ during the melting of the initial mix by the addition of NaBH(4). FCZ-GC contains BaCl(2) nanocrystals formed during the annealing with embedded Sm2+ ions, which dominate PL and XL. The PL of Sm2+ ions embedded in BaCl(2) nanocrystals strongly depends on their crystal structure (hexagonal or orthorhombic) and may be used to identify that structure. The correlation of the PL spectra with X-ray diffraction data is used to estimate the size of nanocrystals. The nanocrystals with average dimensions