The exploration of optoelectronic materials with distinctive properties is still ongoing. To this end, a series of quaternary glassy materials of the composition 15Na2O–65B2O3–(20–x)Bi2O3–xCr2O3, denoted as NBBC, is synthesized using the melt quenching method, where x = 0.0, 2.0, 4.0, 6.0, 8.0, and 10.0 mol%. X-ray diffraction (XRD) confirms that the glasses under investigation are amorphous, except for the sample with a molar ratio of 10% Cr2O3, which showed a polycrystalline structure. FTIR analysis of the NBBC glasses reveals structural changes affecting Bi-O and B-O vibrations, suggesting a correlation between composition and optical properties. Interestingly, the bandgap energy of the NBBC glasses, determined optically, demonstrates a reduction from 2.881 eV to 1.941 eV with increasing Cr2O3 content. Conversely, the tail energy exhibits an opposite trend. The observed reduction in the bandgap with increasing Cr-ions is attributed to the introduction of chromium in the glassy matrix which changes the electronic structure and enhances the light absorption efficiency. Furthermore, various optical parameters are calculated, such as the optical constants, dielectric constants, loss energy, the density of coverage, sheet resistance, the figure of merit factor, and dispersion parameters. Notably, all of these parameters demonstrate a remarkable sensitivity to the gradual increment of chromium ions. These findings imply that the NBBC glasses could be appropriate for optoelectronic purposes.