The influences of the Li⋅⋅⋅π interaction of C6H6⋅⋅⋅LiOH on the H⋅⋅⋅π interaction of C6H6⋅⋅⋅HOX (X=F, Cl, Br, I) and the X⋅⋅⋅π interaction of C6H6⋅⋅⋅XOH (X=Cl, Br, I) are investigated by means of full electronic second-order Møller–Plesset perturbation theory calculations and “quantum theory of atoms in molecules” (QTAIM) studies. The binding energies, binding distances, infrared vibrational frequencies, and electron densities at the bond critical points (BCPs) of the hydrogen bonds and halogen bonds prove that the addition of the Li⋅⋅⋅π interaction to benzene weakens the H⋅⋅⋅π and X⋅⋅⋅π interactions. The influences of the Li⋅⋅⋅π interaction on H⋅⋅⋅π interactions are greater than those on X⋅⋅⋅π interactions; the influences of the H⋅⋅⋅π interactions on the Li⋅⋅⋅π interaction are greater than X⋅⋅⋅π interactions on Li⋅⋅⋅π interaction. The greater the influence of Li⋅⋅⋅π interaction on H/X⋅⋅⋅π interactions, the greater the influences of H/X⋅⋅⋅π interactions on Li⋅⋅⋅π interaction. QTAIM studies show that the intermolecular interactions of C6H6⋅⋅⋅HOX and C6H6⋅⋅⋅XOH are mainly of the π type. The electron densities at the BCPs of hydrogen bonds and halogen bonds decrease on going from bimolecular complexes to termolecular complexes, and the π-electron densities at the BCPs show the same pattern. Natural bond orbital analyses show that the Li⋅⋅⋅π interaction reduces electron transfer from C6H6 to HOX and XOH.