Zinc oxide (ZnO) was embedded in barium and fluorine silicate glass matrices, and luminescence properties of as‐prepared glass samples were studied. For the fluorine‐free glasses, a blue emission was observed. With partial substitution of BaF2 for BaO in glass compositions, emission spectra of glasses show an obvious blue shift to the near‐UV region. For the BaO‐free glasses, the dominant UV emission shifts to the near‐band‐edge exciton emission position of ZnO and also shows a red shift with increasing BaF2. At the same time, a visible emission shoulder appears in the blue to green region and becomes weak with introduction of increasing BaF2.