AbstractGlass forming ability of lone-pair semiconductors was analyzed for (x = 0, 2, 4, 6, 8, 10) system. Values of lone pair electrons L were calculated using average coordination number of valence electrons. These values were found to decrease, as the system was moving towards the rigid region. L > 3 values showed vitreous state. Deviation of the stoichiometry confirmed the chalcogen-rich region. A linear correlation was found between the mean bond energy and glass transition temperature. Chemical Bond Approach model was applied to calculate the cohesive energy of the system. A linear relationship was found to exist between the cohesive energy and the theoretical band gap, calculated using Shimakawa relation. A decrease in both parameters was explained on the basis of average stabilization energy and electronegativity of the system. The density values were found to increase and may account for higher refractive index of the system. Large Bohr radius of the Bi atom accounted for an increase in the polarizability. Other parameters viz. degree of covalency, packing density, compactness, molar volume, free volume percentage, excess volume and polaron radius were also calculated. An effort was made to correlate the effect of Bi addition to Ge12Se76-xAs12Bixlone-pair semiconductor on the basis of the structure of the glassy matrix or the connectedness of the material.