This study reports the preparation and characterization of three new glasses: 75TeO2 - 5Na2O2 - (20-x)BaO –xWO3; labeled as TNB-W00, TNB-W03, and TNB-W10 for x = 0; 3; 10 mol%, respectively. The glasses were prepared using the solid state melt quench procedure. The optical parameters and radiation shielding parameters were estimated by measurement, FLUKA simulations and analytical calculations as required. Prepared glasses were yellowish but transparent in appearance. The density varied from 5.34 to 5.63 gcm-3 for TNB-0 W – TNB-10 W. The band gap decreased from 3.12 to 2.97 eV as WO3 concentration grows. The refractive index increased from 2.36 to 2.40. The minimum (maximum) value of mass attenuation coefficient corresponded to 0.0334 (43.1380) cm2/g for TNB-0 W, 0.0336 (45.9624) cm2/g for TNB-3 W, and 0.034 (57.831) cm2/g for TNB-10 W. Analysis of other parameters showed that WO3 improved the gamma ray shielding ability of the glasses. The stopping power (Sp) of the charged particles (electron, proton, α-particles, and carbon ions) in the glasses with kinetic energy within the spectrum: 0.015−15 MeV calculated using the ESTAR, PSTAR, ASTAR, and the SRIM Monte Carlo code also showed improvement WO3 content. The fast neutron removal cross section equals 0.099 cm-1 for TNB-0 W, while for TNB-3 W and TNB-10, the value is 0.1024 and 0.1047 cm-1 respectively Similarly, the (coherent and incoherent) scattering, absorption, and total cross section of thermal neutrons increased as the WO3 content of the glasses. Compared to some conventional shields, the present glasses present viable, transparent, and lead free alternatives for advanced shielding applications.