A novel copper-catalyzed intermolecular aminoalkynylation of alkenes through a radical relay process has been developed in this work, in which N-fluoro-N-alkylsulfonamides (NFASs) are used as nitrogen-centered radical precursors and alkynyltrimethoxysilanes as alkynylating reagents. This method presents an efficient and straightforward approach to various enantioenriched 2-alkynyl-2-arylethylamines in good yields with excellent enantioselectivity, and these products can be readily converted into a series of synthetically useful chiral terminal alkynes, allenes, alkenes, amines, amino acids, and N-heterocycles.