Glasses have been prepared in the InF3-BiF3-BaF2-PbF2-ZnF2-LnF3 (Ln = Eu, Tm) system. The short-range and medium-range order structure of the glass network is discussed on the basis of IR and Raman spectroscopy data. The effect of bismuth trifluoride on the thermal properties, structure, and photo-luminescence properties of glasses was studied. Bismuth trifluoride doping improves the thermal parameters of glasses. The polyhedra formed by bismuth trifluoride in the glass are not involved in the medium-range order. In rare-earth-containing glasses, strong photoluminescence was discovered in the range 530–560 nm with excitation by the Raman-masking 532-nm wavelength. Bismuth in the glass enhances the europium photoluminescence level in the glass of the InF3-BiF3-BaF2-PbF2-ZnF2-EuF3 system.