Abstract Polyfluoro-2-alkynoic acids, R f C C COOH (R f HCF 2, CF 3, H (CF 2) 3), readily undergo tandem intermolecular-intramolecular Michael addition with bifunctional hetero nucleophiles, HX (CH 2) n, YH (X, Y S, O; n 2, 3), to give 2-polyfluoroalkyl-ated 1, 3-diheterocyclic compounds in good to excellent yields.