This study reports the development of a catalytic asymmetric cationic shift of aliphatic hydrocarbons using imidodiphosphorimidate (IDPi) Brønsted acids. The IDPi catalysts, which are highly acidic and chiral, enable the efficient asymmetric Wagner–Meerwein shift of alkenyl cycloalkanes to cycloalkenes with excellent regio- and enantioselectivity. The reaction proceeds through a highly confined and chiral microenvironment, which stabilizes the carbocation intermediate and enables enantioselective ring expansion. The IDPi catalysts, which are strong and confined acids, suppress olefin isomerization and enable the formation of enantiomerically pure products. The reaction scope was tested with various alkenyl cycloalkanes, including those with branched and substituted alkyl groups, and the results showed high yields and enantioselectivity. The mechanism of the reaction was studied using kinetic and computational methods, revealing that the enantioselectivity arises from non-covalent interactions within the confined chiral pocket. The study demonstrates the potential of IDPi catalysts for asymmetric catalysis of aliphatic hydrocarbons, which are abundant and widely available in chemical synthesis. The results highlight the importance of confinement and acidity in achieving high enantioselectivity in asymmetric catalysis. The study also provides insights into the mechanism of the Wagner–Meerwein shift and the role of the chiral catalyst in enantioselective carbocation rearrangements. The findings have implications for the development of new asymmetric catalytic methods for the synthesis of complex molecules.This study reports the development of a catalytic asymmetric cationic shift of aliphatic hydrocarbons using imidodiphosphorimidate (IDPi) Brønsted acids. The IDPi catalysts, which are highly acidic and chiral, enable the efficient asymmetric Wagner–Meerwein shift of alkenyl cycloalkanes to cycloalkenes with excellent regio- and enantioselectivity. The reaction proceeds through a highly confined and chiral microenvironment, which stabilizes the carbocation intermediate and enables enantioselective ring expansion. The IDPi catalysts, which are strong and confined acids, suppress olefin isomerization and enable the formation of enantiomerically pure products. The reaction scope was tested with various alkenyl cycloalkanes, including those with branched and substituted alkyl groups, and the results showed high yields and enantioselectivity. The mechanism of the reaction was studied using kinetic and computational methods, revealing that the enantioselectivity arises from non-covalent interactions within the confined chiral pocket. The study demonstrates the potential of IDPi catalysts for asymmetric catalysis of aliphatic hydrocarbons, which are abundant and widely available in chemical synthesis. The results highlight the importance of confinement and acidity in achieving high enantioselectivity in asymmetric catalysis. The study also provides insights into the mechanism of the Wagner–Meerwein shift and the role of the chiral catalyst in enantioselective carbocation rearrangements. The findings have implications for the development of new asymmetric catalytic methods for the synthesis of complex molecules.