Three bismuth-borate glasses with the chemical configuration 15Bi2O3-75 H3BO2-10CeO2, 15Bi2O3-75 H3BO2-10Nd2O3, and 15Bi2O3-75 H3BO2-10Sm2O3 and coded as BHB-Ce, BHB-Nd, and BHB-Nd were investigated for their optical and gamma-radiation absorption behaviour. Optical parameters of the glasses such as the molar refractivity, Rm, molar polarizability, αm, reflection loss RL, optical transmission T, metallization criterion M, static dielectric constant εstatic, and optical dielectric constant εoptical were calculated using standard theoretical models. The mass attenuation coefficient μ/ρof the glass samples was estimated by FLUKA simulations and XCOM for discrete photon beams with energies of 0.282, 0.662, 1.33, and 2.51 MeV. The value of Vm was 21.35, 22.61, and 19.60 cm3/mol for BHB-Ce, BHB-Nd, and BHB-Sm, respectively. Also, the highest Rm (16.52 cm3/mol) and αm (6.56 ×10−24 cm3) were obtained for BHB-Ce, while the lowest value was recorded for BHB-Nd (12.035 cm3/mol and 4.78 ×10−24 cm3). Other optical parameters varied with the dopant ion. The photon attenuation coefficient obtained from XCOM calculation and simulations agreed within a 2.90% margin. The μ/ρ varied within the interval 0.0422–0.3086 cm2/g for BHB-Ce, 0.0420–0.3005 cm2/g for BHB-Nd and 0.0420–0.3029 cm2/g for BHB-Sm. The half-value layers (HVLs) vary from 0.3948 cm to 2.8854 cm for BHB-Ce, from 0.3782 cm to 2.7063 cm for BHB-Nd and from 0.3223 cm to 2.3252 cm for BHB-Sm. Based on the values of the photon shielding parameters, the investigated glasses showed better ability to absorb photons compared to conventional shields such as barite concrete, ordinary concrete, and some commercial glass shields. The analysis of the optical and radiation absorption parameters shows that the BHB-glasses are useful in optical and gamma-radiation absorption technologies.