α-Chiral tertiary alkylamines are quintessential scaffolds in pharmaceuticals, bioactive molecules, and organic materials. Although there has been substantial advancement in the synthesis of chiral amides or sulfonamides through open-shell pathway in recent years, it remains problematic to efficiently obtain optically active aliphatic amines, especially α -chiral tertiary alkylamines. Herein, we have demonstrated, by means of density functional theory calculations jointly with experimental studies, that the chiral C–N bond can be forged through a mechanically unprecedented radical cross-coupling of a Cu(I)-bounded dialkyl amine radical species with a carbon-based radical species. Consequently, by virtue of this protocol, a diversity of important optically active β -polyfluoroalkyl substituted α -chiral tertiary alkylamines have been efficiently constructed with high enantioselectivity. • CuH-catalyzed asymmetric reversal hydroamination • Cu-catalyzed enantioselective radical cross-coupling • Efficient construction of β-polyfluoroalkyl-substituted α-chiral tertiary alkylamines • Theoretical mechanistic insight and experimental synthesis A Cu-catalyzed radical cross-coupling of in-situ -generated Cu(I)-bounded dialkyl amine radical species with a carbon-based radical species to create a chiral C–N bond has been disclosed for the first time to our knowledge. By virtue of this approach, asymmetric radical hydroamination of β-aryl substituted polyfluoroalkyl alkenes with hydroxylamine derivatives have been successfully implemented to access an array of important β-polyfluoroalkyl substituted α-chiral tertiary alkylamines in an excellent regio-and enantioselective manner. A Cu-catalyzed radical cross-coupling of in-situ -generated Cu(I)-bounded dialkyl amine radical species with a carbon-based radical species to create a chiral C–N bond has been disclosed for the first time to our knowledge. By virtue of this approach, asymmetric radical hydroamination of β-aryl substituted polyfluoroalkyl alkenes with hydroxylamine derivatives has been successfully implemented to access an array of important β-polyfluoroalkyl substituted α-chiral tertiary alkylamines in an excellent regio- and enantioselective manner.