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Bismuth-germanate glasses, which are well known as a promising active medium for broadband near-infrared spectral range fiber lasers and as an initial matrix for nonlinear optical glass ceramics, have been synthesized in a 5–50 mol% Bi2O3 wide concentration range. Their structural and physical characteristics were studied by Raman and FT-IR spectroscopy, differential scanning calorimetry, X-ray diffraction, optical, and luminescence methods. It has been found that the main structural units of glasses are [BiO6] and [GeO4]. The growth in bismuth oxide content resulted in an increase in density and refractive index. The spectral and luminescent properties of glasses strongly depended on the amount of bismuth active centers. The maximum intensity of IR luminescence has been achieved for the 5Bi2O3-95GeO2 sample. The heat treatment of glasses resulted in the formation of several crystalline phases, the structure and amount of which depended on the initial glass composition. The main phases were non-linear Bi2GeO5 and scintillating Bi4Ge3O12. Comparing with the previous papers dealing with bismuth and germanium oxide-based glasses, we enlarge the range of Bi2O3 concentration up to 50 mol% and decrease the synthesis temperature from 1300 to 1100 °C.