A unique one-pot, high-yield desulfurative-fluorination-bromination reaction which leads to the synthesis of 2,5-dibromo-3-(1,1-difluoroalkyl)thiophenes is reported. A single dithiolane reactant can be used to produce both 2,5-dibromo-3-(1,1-difluoroalkyl)thiophene and 3-(1,1-difluoroalkyl)thiophene with longer alkyl chains.