The new hybrid materials (HM's) are based on the phosphors used in OLED technology in inorganic PbF2-containing matrices: PbF2 powders and low melting PbF2-based oxyfluoride glasses, were synthesized. We used highly effective thermostable phosphors: 4,4,5,5,6,6,7,7,8,8,9,9,9-tridecafluoro-1- (1-methyl-1H-pyrazol-4-yl) nonane-1,3-dione - (1,10-phenanthroline) europium (III), 8-hydroxyquinoline complexes with metals and the individual organic ligand – 4,4,4-trifluoro-1- (2-naphthyl) butane-1,3-dione. Powdered HM's were prepared by co-precipitation from aqueous solutions. The effect of organic molecules or molecular fragments on dimension and morphology of precipitated PbF2 particles, the luminescence properties of HM's were investigated for the samples obtained directly after the precipitation-drying procedure, and after the powders' calcination procedure. The change in the photoluminescence spectra after the heat treatment of the powders is caused by the proceeding of the exchange reaction between the metal complex and the matrix with the formation of Pb-complexes of different coordination is shown. HM (glasses PbF2B2O3, PbF2B2O3SiO2 or PbF2B2O3SiO2ZnO phosphor) were obtained by the melt process in which the phosphor powder was submerged into the melt of the pre-synthesized glasses.