Bismuth based quaternary glasses with compositions BiBLM: 50Bi2O3–20B2O3–15Li2O–15MO (where MO = ZnO, CdO, BaO, and PbO) were processed by conventional melt quenching. The effectiveness of various modifier oxides on the optical and structural properties of the developed glasses was studied systematically by XRD, DSC, FTIR, Raman, and optical absorption (OA) measurements. The synthesized glass specimens were characterized by XRD and the patterns demonstrated an amorphous nature. The physical characteristics such as molar mass, density, and OPD values were found to increase with an increase in the molar mass of the modifier oxides, while there was a decrement in oxygen molar volume, thus resulting in decrement of complete molar volume of the prepared glasses. From DSC analysis, incorrigible reduction and enhancement of Tg and thermal stability among various modifier oxides in the glass network was noticed. Optical absorption data for glass specimens have confirmed the decrease in both direct and indirect optical band gap values among various modifier oxides incorporation. These investigations support the obtained Urbach energy (UE) and metallization criteria of synthesized glasses. The ionic characteristic for the glass specimens were confirmed by the values of electronic polarizability and electronegativity. The Raman and FT-IR spectra of the glass specimens displayed the existence of BiO3, BiO6, ZnO4, CdO4, BaO4, BO3, PbO4, and BO4 structural units within the glass matrix. These structural results can support the applications of as-developed glasses in the area of photonics.