We prepared a series of sodium phosphate glasses by changing WO3/P2O5 content and investigated structure optical and radiation shielding features as a function of glass composition. The average density (ρexp) and was found to increase gradually from 2.49 to 3.07 g/cm3 while the average molar volume values reduced from 47.37 to 44.28 cm3/mol with WO3 addition. Also, the average field strength was also computed and found to increase with increasing WO3. The study of optical absorption spectra reveals that, the absorption peaks in the visible region become higher compared to the peaks In the UV region. This observation is accompanied with a color transformation of glasses from light to dark blue color, with more WO3 adding. The existence of pentavalent tungsten state (W5+) is identified by this blue color. with WO3 addition an absorption band at around at 350–390 nm is appeared. Moreover, this band is overlapped with Urbach edge, which regularly produces an artificial edge-like feature at ~400 nm. A detailed deconvolution protocol is required for an appropriate understanding of these spectra and unravelling the hidden Urbach edge. Our analysis shows that, with increasing WO3/P2O5 content, the optical band gap decreases. This behavior can be elucidated in terms of lower band gap of W (2.7 eV) than that of P2O5 (8.5 eV) and the high polarizing power W. Further, the radiation shielding parameters were investigated for the prepared glasses. WO3 addition improves these shielding parameters against radiation. Where, upon the increase of WO3 concentration, the LAC of glass material increases which leads to a decrease in HVL value. Then it is deducible that the amount of WO3 in this glass sample has an important impact on the shielding capability at lower energy values and has a slight impact at higher energy values.