α-Fluorinated esters were effectively prepared by the Baeyer–Villiger oxidation of α- fluorinated ketones with m-chloroperbenzoic acid (m-CPBA) under mild conditions. The yield of the esters was influenced by the choice of solvent, base, and substituent on the aryl group of the ketones. 4-Methoxyphenyl substituted fluoroketones were oxidized almost quantitatively with m-CPBA within 10min to 12h at room temperature using 1, 1, 1, 3, 3, 3- ...