Glasses in the TeO2single bondPbO·P2O5single bondPbF2:0.5EuF3 system are obtained. The structure, crystallization and luminescent properties are discussed by data of Raman spectroscopy, mainly. It has been demonstrated that a glass network composed of mixed tellurite and phosphate polyhedra is formed in the glasses. Lead difluoride renders a modifying effect on the structure of the glass network at large, i.e., both tellurite and phosphate groups. It has been shown that at the initial stages of the crystallization of the 42.5TeO2single bond32.5PbO·P2O5single bond25PbF2:0.5EuF3 glass the phosphate phases (Pb3(PO4)2) enter into the crystallites. The destruction of the glass network is a partial. The tellurite groups are driven back into the residual glass. At the scattering excitation by a laser with the wavelength λ0 = 532 nm the Eu3 + luminescence corresponding to the emission levels 578, 585, 590, and 612 nm was revealed in glass of the composition 42.5TeO2single bond32.5PbO·P2O5single bond25PbF2:0.5EuF3. The glass crystallization affects the luminescence