EnantioselectiveFriedel–Craftsalkylations of a variety of indoles with ethyl 3,3,3-trifluoropyruvate catalyzed by novel chiral m-phenylenebis(imidazoline)-copper(II) complexes or the bis(imidazoline)-achiral acid combination afforded products with high enantioselectivity. Both enantiomers of indole derivatives can be prepared with high enantioselectivities by tuning the N-substituents of the imidazoline