This Letter presents the first examples of hetero-Diels–Alder reactions of polyfluoroalkanethiocarboxylic acid amides and 2,3-dimethylbutadiene under microwave heating. Cycloaddition reactions proved to be dependent on the nature of perfluoroalkyl chain and on the substituents attached to the nitrogen atom. Formation of ammonium salts was also performed by simple treatment of the corresponding cycloadducts with trifluoromethanesulfonic acid. In the case of octafluorobutyl-substituted derivative, one spontaneous desamination reaction took place leading to new 2H-thiopyran.