Investigation of CO2 transformation into value-added organic molecules is an interesting purpose in scientific communities. Here, the substitute effect exploration in CO2 incorporation reaction toward benzoxazinones formation, as a bioactive heterocyclic compound, is the main studied issue. A profound understanding of the substituent effect is helpful toward the investigation of the kinetic and thermodynamic aspects of the reaction. The substituted arynes, an imine compound, and atmospheric CO2 have been reported as the starting reactants. The substituted functional groups show substantial consequences on the studied mechanisms. The obtained results show that mechanism A, in which the imine compound is added as a nucleophile to arynes, is the most probable mechanism. The Energetic Span Model (ESM) was used in the kinetic studies, which indicates the turnover-frequency determining intermediate (TDI) and turnover-frequency determining transition state (TDTS) in the reaction progress. Also, Electron localization function (ELF) analyses reveal that the electron density of a developing monosynaptic basin on the carbon atom (V(C)) at the transition state shows a good linear correlation with the calculated energy values of TDTS. Electron-withdrawing and electron-releasing characters of the substituents have the main effects on the electron density of the developing basin at the transition states which change the TDTS energies.