Glasses with WO3 in place of CaO with the chemical formula 45B2O3+15TeO2+(18-X)CaO+22Na2O + XWO3: X = 0 (W-0), 1.5 (W-1.5), 3 (W-3), 4.5 (W-4.5), and 6 (W-6) mol% were prepared using the melt quenching method. A comprehensive study of the structural, physical, optical, and γ-ray protection properties of the prepared glasses was investigated. Density (ρ), molar volume (Vm), UV–Vis measurements, the MCNP5 simulation code, and PhX software were employed to achieve the aims of this study. The density (ρ) of the W-X samples increased slightly from 2.45 g/cm3 to 2.62 g/cm3 as WO3 content increased from 0 to 6 mol%. The molar volume (Vm) evinced the same trend as ρ. In the UV range, significant absorption was observed, rising as the molar concentration of WO3 increased. The direct optical gap (Eopt.(dir.)) declined from 3.59 eV to 3.24 eV, while the indirect gap (Eopt.(indir.)) declined from 3.27 eV to 2.36 eV. The Urbach energies (ΔE) ranged from 0.35 to 0.71 eV. The refractive index (n) increased from 2.33 to 2.59 as WO3 content increased. The molar polarizability (αm) and molar refractivity (Rm) increased. The linear-attenuation absorption (μ) order is: W-0 < W-1.5 < W-3 < W-4.5 < W-6. The W-6 glass sample possessed the lowest half- (HVL), and tenth- (TVL) value layer, as well as the lowest mean free path (MFP). Therefore, the W-6 glass sample offers the best gamma radiation shielding capability among the prepared W-X glasses. Within the investigated energy range, the effective atomic number (Zef) varied from 30.773 to 13.234, 35.398–13.969, 39.089–14.670, 42.103–15.338, and 44.611–15.977 for the W-0, W-1.5, W-3, W-4.5, and W-6 glasses, respectively. At 0.080 MeV, the mass-attenuation absorption (μm) of the investigated W-X glasses was higher than for TBLMC-X (TeO2–B2O3–Li2O–MoO3–CuO) and TS-X (9SiO2–Al2O3–Na2O–B2O3–TeO2) glasses.