Glasses in SiO2–ZnO–BaO system with the different ZnO/BaO ratio were studied. In some cases, BaF2 was introduced to substitute for BaO on the equal base. Photoluminescent spectra showed that ZnO in glass matrices behaved somewhat differently from ZnO crystals. Especially, the introduction of fluorine ions led to dramatic shift of UV emission band of glasses closer to that of ZnO crystals. Raman spectral analysis provided consistent results. In particular, Raman bands in the high frequency region are sensitive to effects of different ZnO/BaO or BaF2/BaO ratio on structure of glasses.