The generation of thioesters through thioesterification of carboxylic acid has significant synthetic value given the easy availability of various carboxylic acids and the extensive application of thioesters. An economical and rapid thioester synthesis approach is still needed. Herein, we achieved thioesterification of carboxylic acids with valuable glycosyl thiol, aromatic and aliphatic thiols mediated by sulfonyl fluoride (SO2F2). The compatibility of numerous carboxylic acid substrates was tested, including (hetero)aromatic and aliphatic carboxylic acids and the reaction proceeded smoothly under mild conditions at good yields. Late-stage modification of drug molecules rac-Naproxen and Loxoprofen proved feasible. Besides, the gram-scale reaction demonstrated the utility of this protocol.