In this study, a novel series of nano-Sm2O3-doped lithium borotellurite glasses was synthesized and systematically investigated in terms of their structural, physical, and radiation shielding characteristics. X-ray diffraction confirmed the amorphous nature of all samples, while transmission electron microscopy revealed progressive nanoarchitectural refinement and particle growth with increasing Sm2O3 content, from uniformly dispersed nanodomains to dense agglomerates exhibiting short-range crystalline ordering. Energy-dispersive X-ray spectroscopy and elemental mapping validated the homogeneous incorporation of boron, oxygen, tellurium, and samarium throughout the glass matrix without phase separation. Gamma-ray shielding evaluations showed enhanced mass attenuation coefficients and reduced half-value layers, particularly in the Sm(n)8 sample, with significant performance gains at lower photon energies. Neutron shielding assessments further indicated elevated macroscopic removal cross-section values and dose attenuation, affirming the compositional benefit of Sm2O3 for fast neutron mitigation. It can be concluded that nano-Sm2O3 incorporation would play a multifunctional role on structural and radioprotective properties in addition to morphostructural features of lithium borotellurite glasses.