Impressive progress has been made in the copper‐catalyzed asymmetric propargylic substitution (APS) reaction, but its use in remote asymmetric yne‐allylic substitution remains a challenging topic. Herein, we report the first remote enantioselective copper‐catalyzed sulfonylation of yne‐allylic esters with sodium sulfinates. The reaction is assumed to occur via a copper‐vinylvinylidene species as the key reactive intermediate. The use of readily available starting materials, the mild reaction conditions, and the excellent regio‐, enantio‐ and stereoselectivity, as well as broad substrate scope (>70 examples), show the practicality and attractiveness of this method. An enantioselective copper‐catalyzed reaction was developed for the sulfonylation of yne‐allylic esters with sodium sulfinates. Salient features of this practical method include readily available starting materials, mild reaction conditions, excellent regio‐, enantio‐ and diastereoselectivity, as well as broad substrate scope.