Cross-dehydrogenative coupling (CDC) has emerged as a powerful synthetic method for the straightforward and efficient construction of C–C and C–heteroatom bonds. In particular, asymmetric versions of this reaction are highly desirable, since they would provide a simple approach to complex molecules from simple materials without any prefunctionalization of substrates. In recent years, great achievements have been made in this area, and many powerful approaches have been developed for this transformation with high enantioselectivity. In this account, we summarize recent advances in the enantioselective oxidative α-C(sp³)–H bond functionalization of amines according to the catalytic reaction systems. Moreover, the catalytic mechanisms of the asymmetric oxidative reactions are also discussed.