Heating a DMSO solution of 4-(perfluoro-n-alkyl)-4-hydroxy-2,5-cyclohexadien-1-one (4-perfluoroalkyl-4-quinols) in the presence of a catalytic amount of base brought about 1,2-migration of the perfluoroalkyl group to give 2-(perfluoro-n-alkyl)hydroquinone or 5-(perfluoro-n-alkyl)-2-cyclohexene-1,4-dione depending upon the substitution pattern of the quinol. The similar rearrangement of 4-perfluoroisopropyl-4-hydroxy-2,5-cyclohexadien-1-one occurred very smoothly at room temperature under the basic conditions. 5-Hydroxy-4-methyl-5-perfluorooctyl-1-propyl-3-pyrrolin-2-one underwent the base-induced rearrangement to afford a perfluorooctylated succinimide derivative. On the other hand, 5-hydroxy-3-methyl-5-perfluorooctyl-1-propyl-3-pyrrolin-2-one and 5-hydroxy-1-isobutyl-5-perfluorooctyl-3-pyrrolin-2-one did not suffer any rearrangement, although their structures were very similar to the 4-methylated one.