A glass system was prepared according to the formula 60mol%B2O3 – x mol %barite – (40-x) mol %Li2O, where x=0, 5, 7.5, 10, 15 and 20 mol%. The amorphous nature of the prepared glasses was confirmed through X-ray diffraction. The prepared glasses were also characterized by FTIR spectroscopy, UV-vis absorption spectroscopy and the differential thermal analysis (DTA). The density is found to increase and this is because of the higher molecular of the added barite. The molar volume also increases with increasing barite content that indicates the structural changes occurred in borate network that were also confirmed using FTIR. Increasing the concentration of barite shifts the UV cutoff edge toward higher wavelengths from about 300 nm at 0 mol% barite to about 400 nm at 15 mol% of barite. Glass transition temperature (Tg) is found to increase with the increasing barite content. When analyzed by photoluminescence, the samples exhibit luminescence emission centered at around 400, 415, 480, 430, 485, 520, 545, and 570 nm when excited at 300 nm wavelength. The emission peaks at 420 nm, and 440 nm were assigned to F center emission. Between 440 nm and 520 nm it is rather the effect of the presence of the impurities.