The combination of high optical transparency and radiation shielding effectiveness of zinc sodium borate glasses by tungsten oxide additions has been investigated. We investigated glasses of a formula [xWO3–(25-x)-ZnO-20Na2O–55B2O3; where 0 ≤x ≤ 20, step= 5 mol. %], based on their structural, optical and radiation shielding properties. Actually, five different glass samples were synthesized using the melt quenching approach. The transmittance of all glass samples was measured via a spectrophotometer in the wavelength range from 300 to 1100 nm. The transmittance results confirmed the increased transparency of the investigated glasses with further WO3 additions. Moreover, the transmittance results indicated the absence of W5+, W4+, W3+ states; based on the absence of their absorption bands. Furthermore, these transmittance results revealed that the only oxidation state in the present glasses is the hexavalent tungsten (W6+) that belongs to the d° electronic configuration. The refractive index (n0) and nonlinear refractive index (n2) were determined and showed an increasing behavior with further WO3 doping. Also, the additions of WO3 resulted in an increasing behavior in the linear attenuation coefficient values with a decreasing one in the half-value layer of the current glasses. These outcomes declare that the current glasses are good candidates for radiation shielding purposes.