Lead-barium fluoroborate glasses doped with RE are synthesized. Using the heat-treatment (HT) glass-ceramics in which RE 3þ (Eu 3þ or Er 3þ ) ions are building into fluoride crystalline nanoparticles homogeneously distributed in the borate glass matrix are made. The changes in the structural and optical properties of the glass-ceramics comparatively to initial glasses and polycrystalline fluoride containing Pb, Ba, and RE are revealed by X-ray diffraction and luminescence spectroscopy of RE ions.