Deoxygenative syntheses of fluorinated thioesters directly from carboxylic acids have been developed employing benzothiazolium reagents. The process using BT-SCF3 represents an attractive approach toward these SCF3-containing compounds that avoids the use of metal -SCF3 salts or preactivated acyl electrophiles. Moreover, the in situ activation of BT-SCF2H allows for an unprecedented nucleophilic difluoromethylthiolation reaction. DFT calculations support a mechanistic scenario involving a four-membered transition state where acyl substitution occurs without the formation of an unstable free -SCF2H anion.