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In this work structural and luminescence properties of gallo-germanate glasses were investigated. The mentioned glass system was modified with barium and antimony oxides and doped with Eu3+ ions. The starting glass consisted of barium oxide as a modifier which was then gradually replaced by antimony oxide to form six glass samples. The gallo-germanate glass as a low-phonon host for RE (Rare Earths) ions is a promising material for optoelectronics. However, luminescence properties closely depend on material composition. For this reason, structural changes in studied materials were induced by changing its chemical composition and the luminescence properties were tested. The FT-IR (Fourier-Transform Infrared Spectroscopy) and the Raman spectra of studied glasses illustrate the tendency to increasing quantity of bridging oxygen connecting germanium ions and decreasing quantity of non-bridging oxygen along with antimony oxide addition. Simultaneously the BP (Boson Peak) measurements and emission spectra of Eu3+ ions show an increasing tendency to the examined glass structure ordering along with modifier oxide addition. [ABSTRACT FROM AUTHOR]