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In this study, the optical and gamma ray shielding properties of vanadotellurite-based quaternary glasses in the xNa2O-(20-x)K2O-30V2O5-50TeO2 system were examined. The optical band gap (Eopt) displayed an initial reduction from 2.33 to 2.30 eV (x ≤ 10 mol%), before increasing from 2.31 to 2.39 eV for x > 10 mol%, which indicated a change in non-bridging oxygen (NBO) concentration. There is an inverse relationship between Urbach energy (Eu) and Eopt. The refractive index (n) also showed an off-trend pattern within the same area (x = 10 mol%), which indicated a difference in polarizability due to changes in BO and NBO concentrations. The Phy-X software was used to analyse the radiation attenuation competence for the investigated glass systems. For the total interaction of photons between the 0.284 to 2.506 MeV energy range, the linear attenuation coefficients (LAC), the radiation protection efficiency (RPE), half-value layers (HVL) and mean free path (MFP) were determined. The increased Na2O content increased the values of LAC and RPE. The results demonstrated that the 20Na2O-30V2O5-50TeO2 composition had the most desired photon shielding properties.