The reactions of 3-perfluoroacyl-4Н-chromenes and 2-perfluoroacyl-1Н-benzo[f]chromenes with primary aromatic amines resulted in pyran ring cleavage, which was initiated by an aza-Michael reaction. The obtained enamino ketones underwent rearrangements in the presence of superacids, giving 2-perfluoroalkyl-4Н-chromene-3-carbaldehydes and 3-perfluoroalkyl-1Н-benzo[f]chromene-2-carbaldehydes, respectively.