The article describes a novel catalytic asymmetric Wagner–Meerwein shift reaction for aliphatic alkanyl cycloalkanes, enabling the conversion of these substrates into cycloalkenes with excellent regio- and enantioselectivity. This reaction, catalyzed by imidodiphosphorimidate (IDPI) acids, is the first to achieve asymmetric catalysis with purely aliphatic hydrocarbons, which have traditionally been challenging to handle in asymmetric catalysis due to their lack of heteroatoms or aromatic groups. The study demonstrates the potential of IDPI catalysts in processing unbiased substrates and highlights their ability to suppress olefin isomerization, leading to high yields and enantioselectivities. The mechanism involves protonation of the olefin, followed by a five- to six-membered ring expansion, and finally, deprotonation to form the final product. Computational studies support the proposed mechanism, showing that the rate-determining step is protonation, and enantioselectivity is influenced by non-covalent interactions within the confined chiral pocket. This work opens new avenues for the asymmetric catalysis of aliphatic hydrocarbons.The article describes a novel catalytic asymmetric Wagner–Meerwein shift reaction for aliphatic alkanyl cycloalkanes, enabling the conversion of these substrates into cycloalkenes with excellent regio- and enantioselectivity. This reaction, catalyzed by imidodiphosphorimidate (IDPI) acids, is the first to achieve asymmetric catalysis with purely aliphatic hydrocarbons, which have traditionally been challenging to handle in asymmetric catalysis due to their lack of heteroatoms or aromatic groups. The study demonstrates the potential of IDPI catalysts in processing unbiased substrates and highlights their ability to suppress olefin isomerization, leading to high yields and enantioselectivities. The mechanism involves protonation of the olefin, followed by a five- to six-membered ring expansion, and finally, deprotonation to form the final product. Computational studies support the proposed mechanism, showing that the rate-determining step is protonation, and enantioselectivity is influenced by non-covalent interactions within the confined chiral pocket. This work opens new avenues for the asymmetric catalysis of aliphatic hydrocarbons.