Herein, we report the metal-free hydration of pyridine-SF4-alkynes, under acidic conditions and with reaction durations ranging from 5 min to 10 h at room temperature, to synthesize pyridine-SF4-methyl ketones in yields of 59-93%. Further, we demonstrate the synthetic applications of the synthesized pyridine-SF4-methyl ketones, such as chlorination, NaBH4 reduction, Baeyer-Villiger oxidation, and the generation of enol-triflates. These compounds hold promise as useful building blocks in the syntheses of a wide range of SF4-containing drug candidates.