Enantiopure aziridines are versatile chiral building blocks that have a high potential for further elaboration to a wide range of chiral nitrogen-containing derivatives. The aziridine ring is not only an important reactive intermediate but is also present in many biologically active compounds. In the context of an explosion of research in organofluorine chemistry due to the matchless properties of fluorinated molecules, trifluoromethylated building blocks are privileged scaffolds for library design and drug discovery. Herein, we report the first catalytic asymmetric synthesis of CF3-substituted aziridines that is remarkable for its simplicity, a low catalyst loading, and very high enantioselectivity.