Aliphatic compounds substituted with medicinally‐important trifluoromethylthio (SCF3) and trifluoromethylselenyl (SeCF3) groups have been synthesized directly from alcohols using the new benzothiazolium salts BT‐SCF3 and BT‐SeCF3. These bench‐stable fluorine‐containing reagents are facile to use and can be prepared in two steps from non‐fluorinated heteroaromatic starting materials. The metal‐free deoxytrifluoromethylthiolation process using BT‐SCF3 proceeds under mild conditions while the similarly efficient trifluoromethylselenylation reactions using BT‐SeCF3 are, to the best of our knowledge, the first reported examples of this transformation.