Using the melting-quench technique, a new method for removing bypass cement dust (BCD) was developed in this study using an active environmental glassy system with the chemical formula (65–x)B2O3–5Li2O–5CdO–25BCD–xBi2O3, where x varied from 0 to 30 mol%. A glass density of 3.137 g/cm³ is attained without bismuth, while a density of 5.345 g/cm³ is obtained with 30 mol% Bi2O3. The unit peaks BO3 and BO4 in the FTIR spectra signify the presence of the BLCDBi-series structure. Elevated Bi2O3 concentrations augment BO4 units. Defects influence the optical absorbance of glass within the wavelength range of 190–1000 nm. These defects in the glass network are created by silicon electrons, silicon hole centers, and BCD as well as Bi3+ or Bi6+ after the addition of bismuth oxide to the glassy system. Eg values were found to decrease as Bi2O3 concentration increased, whereas EU and n values exhibited the opposite behavior. A gamma spectroscopy system and the Phy-X/PSD software are used to calculate the linear attenuation coefficient (LAC), mass attenuation coefficient (MAC), half-value layer (HVL), tenth-value layer (TVL), effective atomic number (Zeff), and effective electron density (Neff) of samples. In addition, the Phy-X/PSD software demonstrated good agreement between experimental and theoretical interpretations. Overall, the results showed that the BLCDBi-30 sample is suitable for use in radiation protection.