The π-π stacking interactions in the Ben||substituted-coronene and HFBen||substituted-coronene complexes was studied using the computational quantum chemistry methods (where Ben and HFBen are Benzene and Hexafluorobenzene, || denotes π-π stacking interaction, substituted-coronene is coronene molecule which substituted with four X groups, and X= NH₂, CH₃, OH, H, F, CN, and NO). The results reveal effects of substituents and opposite nature of Ben and HFBen on the π-π stacking interactions in complexes which direct electrostatic interactions of substituents on one ring don’t manipulate π electron cloud of the other ring. Electron-withdrawing/electron-donating substituents lead to better binding energies in the Ben||substituted-coronene/HFBen||substituted-coronene complexes. Atoms in molecules (AIM) analysis and charge transfer (CT) effects, also relationships between through-space spin-spin coupling constants, J_C-C and J_C-F, and π-π stacking binding energies were studied in the Ben||substituted-coronene and HFBen||substituted-coronene complexes.