A simple and efficient synthesis to both enantiomers of highly enantiomerically enriched α-trifluoromethyl-α-(heteroaryl)-glycine derivatives via highly stereoselective aminoalkylation of indoles and pyrroles is described. The triflic acid-catalyzed reaction of enantiomeric 3,3,3-trifluoro-pyruvate-α-methylbenzyl imines with indoles and pyrroles and the subsequent Pd-catalyzed hydrogenolysis of the methylbenzyl group provided the products in high yields and excellent enantioselectivities.