The asymmetric Mannich reaction of 2-fluoroindanone with ketimine was developed under the catalysis of a kind of chiral copper complex, affording a chiral tetrahedral center containing fluorine. A series of β-fluoroamine derivatives can be obtained in excellent yields (73-94%) with high diastereoselectivities (>99:1 dr) and enantioselectivities (89-99%). The possible transition state was supported by density functional theory calculation.