Herein, we describe an efficient, practical free-metal rapid access to active hexafluoroisopropyl benzoates from anthranils, hexafluoroisopropanol, and N-alkoxy α-halogenoacetamides. Notably, this process includes anthranils that underwent a distinct pattern reaction. The protocol has good functional group tolerance and a broad substrate scope. Using a simple and general method, we accomplished potential synthetic application of active ester.