In the presence of BF3·OEt2, (perfluoroalkyl)lithiums generated in situ from the reaction of primary perfluoroalkyl iodides and MeLi_‒LiBr reacted with imines, azines, and nitrones to afford perfluoroalkylated nitrogen-containing compounds in moderate to good yields. This method was successfully applied to the preparation of a (perfluoroalkyl) glycine and optically active perfluoroalkylated amines. © 1992, American Chemical Society. All rights reserved.