Pentafluoropropen-2-ol (PFP) was prepared by the reaction of hexafluoroacetone (HFA) with Mg/TMSCl.The one-pot tandem sequential reactions of PFP via Mannich addition with aldimines followed by Friedel−Crafts cyclization and aromatization afforded the title quinolines. A variety of corresponding 3-substitutedquinolines were derived from the title quinoline by nucleophilic substitution of 3-fluorine with nucleophiles.A defluorinative transformation of the 4-trifluoromethyl group of the title quinoline with hydrazine affordedpyrazoloquinoline.