The series of SiO2-Bi2O3-PbO-ZnO-BaO and SiO2-TiO2-Bi2O3-PbO-Na2O glasses were synthetized to obtain non-crystallizing materials, dedicated to fabrication of photonic crystal fibers. During composition development, the thermal properties were investigated according to the change of chemical composition. The glasses contain high concentrations of heavy metal oxides for high refractive index, large nonlinear refractive index and spectrally broad transmission window from 0.5 to 4.5 μm. Their thermal properties are optimized to enable drawing of all-solid glass photonic crystal fibers in tandem with previously designed highly nonlinear glass PBG81 based on SiO2-Ga2O3-Bi2O3-PbO-CdO system. This creates novel dual glass combinations for PCF fibers. We have also investigated influence of melting conditions on the final thermal and optical properties, including absorption from water contamination at around 2.8 μm.