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Different B 2 O 3 content was added to Ce3+–doped Gd 2 O 3 –Al 2 O 3 –SiO 2 (xBGAS:1.1Ce3+, x = 0, 5, 10, 15) glasses to improve the photoluminescence (PL) and scintillation properties. The transmittance of 15BGAS:1.1Ce3+ glass is over 80%. The X–ray absorption near edge spectroscopy (XANES) spectra imply that Ce4+ can be effectively reduced to Ce3+ in the glasses by adding Si 3 N 4. The excitation and emission spectra show a blue shift with increase of B 2 O 3 content. The photoluminescence quantum yield (PL QY) increases with the increase of B 2 O 3 content, reached the maximum of 59.55% when x = 15. The PL decay time of the glasses exhibits typical values (44–50 ns) due to 5d→4f transition of Ce3+ ions. The PL thermal activation energy become larger, indicating that xBGAS:1.1Ce3+ glasses have better luminescent thermal stability. The integral X–ray excited luminescence (XEL) intensity of the 15BGAS:1.1Ce3+ glass is 37.38% of Bi 4 Ge 3 O 12 (BGO) crystal, and the light yield is 1267 ph/MeV with an energy resolution of 23.22% at 662 keV when exposed to γ–rays. With the increase of B 2 O 3 content, the fast component of scintillation decay time gradually becomes shorter and the slow component becomes longer. The thermally stimulated luminescence (TSL) curves were measured to investigate the trap depth and density of defects in xBGAS:1.1Ce3+ glasses. [ABSTRACT FROM AUTHOR]