Glasses with composition [xWO3–(25−x)–ZnO–20Na2O–55B2O3 where x = 0, 5, 10, 15 and 20 mol. %] were prepared by melt quenching method. The amorphous state of the current glass samples was checked by X-ray difraction (XRD). The measured density and calculated molar volume of all prepared samples were found to increase with the replacement of the lighter ZnO by the heavier of WO3. The network structure of the present glasses was studied using the infrared (IR) and Raman spectroscopic techniques. IR and Raman results show that the structure of the samples is BO3 and BO4 units located in several structural groups with W–O–W units. The decreasing of the band gap energy values by the introducing of WO3 showed that the creation increases of the number of non-bridging oxygens in the structure of glass. All results showed that the parameters were dependent upon the dopant concentration of WO3 in the prepared glasses.