The present report details the results of a high-level theoretical investigation of benzene-AlX3 and ethene-AlX3 (X = Il, F, CI) interactions. The binding energies, preferred modes of interaction of AlX3 with benzene and ethene, and vibrational frequencies for these complexes have been evaluated at the MP2 level using basis sets ranging from the 6-31+G* to the much larger (6-311++G(2df,p) + diffuse(d,p)). In the lowest energy conformers of the benzene complexes, the Al atom is directly placed over one of the benzene carbons, while in the ethene complexes, the Al atom lies above the center of the pi bond. The binding energies of both the benzene and ethene complexes of AlX3 an dominated by electrostatic contributions, which is in contrast to the dominance of the electron correlation energy in the benzene-BX3 complexes. A very sharp increase in the negative charge of the benzene carbon closest to the Al atom in the lowest energy conformers of the benzene complexes from -0.2 to -0.4 an points to an important role of activation of the aromatic ring by the Lewis acid in electrophilic aromatic substitution reactions.