A novel asymmetric radical aminotrifluoromethylation of alkenes has been developed for the first time, providing straightforward access to densely functionalized CF3-containing azaheterocydes bearing an alpha-tertiary stereocenter with excellent enantioselectivity. The key to success is not only the introduction of a Cu(I) / chiral phosphoric acid dual-catalytic system but also the use of urea with two acidic N-H as both the nudeophile and directing group. The utility of this method is illustrated by facile transformations of the products into other important compounds useful in organic synthesis and medicinal chemistry.