Incorporation of fluorinated heterocyclic framework into organic molecules results in profound changes in their physical, chemical and biological properties. Realizing that the fluorinated thiochroman-4-ones are important scaffolds in medicinal chemistry and are rare in the chemical literature, one-pot synthesis of 2-/3-(trifluoromethyl)thiochroman-4-ones was attempted. Direct access to 2-/3-(trifluoromethyl)thiochroman-4-ones was achieved by a tandem alkylation-cyclic acylation process promoted by superelectrophilic activation of 2-/3-(trifluoromethyl)acrylic acid in superacidic trifluoromethanesulfonic acid under microwave-assisted Friedel-Crafts alkylation of benzenethiols followed by cyclization (via intramolecular acylation). Synthesis of a series of 2-/3-(trifluoromethyl)thiochroman-4-ones from protosolvated 2-/3-(trifluoromethyl)acrylic acid intermediates and benzenethiols is described.