The lithium aluminosilicate scintillation glasses doped with different concentrations of Tb3+ ions were prepared by the melt quenching method. Photoluminescence properties were characterized by UV excitation, emission and fluorescence lifetime, and radio luminescence properties were measured by X-ray and cathode-ray excitation. The results show that the cross relaxation between Tb3+ ions increased with increasing the doping concentration of Tb3+ ions in the case of low concentration of Tb3+, which resulted from the energy of 5D3 →7Fj transition transfers to 5D4→7Fj transition, so it leads to the fluorescence lifetime and emission intensity of 5D3 excited state decreasing. The emission intensity of 5D4→7Fj increasing. When the concentration of Tb3+ ions continued to increase in higher concentration of Tb3+ ions, the nonradiative transition would be increased, which was the main reason for the decrease of fluorescence lifetime and emission intensity of 5D4 excited state. It can be found that the energy transfer from 5D3 energy level to 5D4 energy level was increased with the increasing energy of excitation source by comparing the photoluminescence and radioluminescence, which is due to that the density of the glass was low.