4,5-Dihydroxy-4,5-bis(trifluoromethyl)imidazolidin-2-one and its N-methyl(phenyl)-substituted analogous were synthesized by the reaction of perfluorobiacetyl with urea and methyl(phenyl)urea. Depending on a solvent nature and character of the substituent at N-atom of the imidazolidine, different trifluoromethyl-containing heterocycles were obtained in reactions of the imidazolidin-2-ones with thiosemicarbazide and guanidine carbonate: imidazothiazol, 1,2,4-triazines, and hydantoins.