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.