The utilization of β-fluoroamines as pharmaceutical components for drug development has attracted a considerable amount of interest. However, direct access to tertiary β-fluoroamines is challenging. We herein report the rhodium-catalyzed asymmetric amination of tertiary allylic trichloroacetimidates with anilines and cyclic aliphatic amines to access tertiary β-fluoroamines, where the α-carbon atom is bonded to four different substituents, in good yield with high levels of enantioselectivity.