A chiral α-sulfinyl α, β-unsaturated ketone served as a good chiral diene or enophile in intramolecular Lewis acid-catalyzed asymmetric pericyclic reactions, giving hetero-Diels-Alder reaction products, together with ene reaction products in some cases, in high optical yields. The reaction pathways for Diels-Alder or ene reactions were readily controlled depending on the Lewis acids used. A chiral α-sulfinyl α, β-unsaturated ester served as a good enophile to give ene reaction products with high enantioselectivity. The mechanistic pathway for the asymmetric induction is proposed on the basis of the stereochemical results obtained.