For Ge-Se-Bi glassy chalcogenides, the influence of increasing Bi content on physical properties such as ionicity and covalent character of some combinations, number of constraints, average coordination number (CN), average heat of atomization (Hs), cross-linking density (X), the stoichiometry of the compositions (R), lone-pair electrons (L), glass transition temperature (Tg), and so on has been theoretically investigated. In this work, we examined the addition of Bi content in Ge18BixSe82-x glassy alloys for (x: 0.5, 2, 4, 6, and 8 at. %) and correlated the physical parameters to theoretical predictions. Cross-linking of chains, average coordination number (CN), mean bond energy, glass transition temperature, and values of Nc and X all rise as the concentration of Bi increases from 0.5 to 8%, whereas average heat of atomization (Hs) drops. The current system is consistent with prior studies, which found that a system with a substantial number of lone-pair electrons is a stable state.