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A novel series of glass, consisting of B2O3, Bi2O3, TeO2, and TiO2 (BBTT) containing rare earth oxide RE2O3, where RE is La, Ce, Sm, Er, and Yb, was prepared. We investigated the structural, optical, and gamma attenuation properties of the resultant glass. The optical energy bands, the linear refractive indices, the molar refractions, the metallization criteria, and the optical basicity were all determined for the prepared glass. Furthermore, physical parameters such as the density, the molar volume, the oxygen molar volume, and the oxygen packing density of the prepared glass, were computed. Both the values of density and optical energy of the prepared glass increased in the order of La2O3, Ce2O3, Sm2O3, Er2O3, and then Yb2O3. In addition, the glass doped with Yb2O3 had the lowest refractive index, electronic polarizability, and optical basicity values compared with the other prepared glass. The structures of the prepared glass were investigated by the deconvolution of infrared spectroscopy, which determined that TeO4, TeO3, BO4, BO3, BiO6, and TiO4 units had formed. Furthermore, the structural changes in glass are related to the ratio of the intensity of TeO4/TeO3, depending on the type of rare earth. It is also clarified that the resultant glass samples are good attenuators against low-energy radiation, especially those that modified by Yb2O3, which exhibited superior shielding efficiency at energies of 622, 1170, and 1330 keV. The optical and gamma ray spectroscopy results of the prepared glass show that it is a good candidate for nonlinear optical fibers, laser solid material, and optical shielding protection. [ABSTRACT FROM AUTHOR]