This study aimed to investigate different types of glasses based on 50TeO2–30B2O3–(20-x)Li2O-xGd2O3 (x = 0, 5, 10, 15, 20 mol.%) system in terms of their structural, optical, physical properties. Accordingly, five different samples were fabricated using melting-annealing method. Density calculations of the synthesized glasses were performed by using Archiemedes principle. Structural, optical, physical and radiation interaction properties were characterized through the XRD analyses, Raman spectra along with optical band gap, refractive index and Urbach energy and advanced simulation methods. Increasing Gd2O3 reinforcement from 0% to 20% mole increased glass density from 4.065 gcm−3 to 5.430 gcm−3. Optical transmittance as well as absorption parameters varied almost monotonically with increasing ratios of Gd2O3 indicating the ability to estimate and control these properties using Gd2O3 additive. Substitution of Li2O with Gd2O3 within the structure increased the optical band gap significantly. The results showed that TBLG20 sample with the highest Gd2O3 additive has the highest gamma-ray and charged particle attenuation properties. It can be concluded inserting of high concentration Gd2O3 to TeO2–B2O3–Li2O glass system is useful synergetic tool of combining structural, optical, and radiation characteristics.