Bioactive glasses are renowned for their applications in dentistry, serving as restorative materials, dental adhesives, intracanal medicaments, and agents for enamel remineralization. Niobium pentoxide (Nb2O5) is employed in dental adhesive resins and orthodontic adhesives, offering radio-pacifying properties essential for dental materials. Samarium oxide (Sm2O3) emerges as a potential additive in aesthetic restorative dental ceramics and resins, enhancing the natural fluorescence of teeth. In this study Nb2O5 and Sm2O3-doped (1, 3, and 5 wt%) 13–93 bioactive glass particles were synthesized via the sol-gel method, tailored for dental implementations. We conducted a comprehensive analysis of the physical, structural, and optical properties of the resultant glass powders. Additionally, their in vitro bioactivity and ionizing radiation shielding characteristics were rigorously evaluated. The results indicate that Sm3+ ions preserve the amorphous nature of the silicate glasses, while Nb5+ incorporation leads to the crystallization of the T-Nb2O5 phase. Bioactivity assays across three physiological fluids—simulated body fluid, α-minimum essential medium, and phosphate-buffered saline, demonstrated the ability of doped glasses to facilitate hydroxyapatite layer formation, with the most pronounced bioactivity observed in phosphate-buffered saline immersed samples. Furthermore, radiation shielding simulations reveal that the addition of Nb2O5 and Sm2O3 enhances the ionizing radiation attenuation capabilities of the glasses, a property that holds significant promise for protecting against radiation in dental radiology. It can be concluded that the dual functionality of Nb5+ and Sm3+-doped bioactive glasses, which may revolutionize restorative dental practices and offer improved protection in radiological applications.