Perfluoro(2-propoxypropionyl) fluoride (1a), which is the precursor of the perfluorinated propyl vinyl ether (PPVE) monomer of an industrially important perfluoroalkoxy copolymer (PFA), was synthesized by utilizing direct fluorination of the non-fluorinated counterpart for the first time. The partially-fluorinated ester 7 synthesized from the desired perfluorinated acid fluoride la itself and the non-fluorinated alcohol 5, which has a carbon skeleton corresponding to the desired compound 1a, was perfluorinated by liquid-phase direct fluorination with elemental fluorine. Degradation of the resulting perfluorinated ester 8 gave 2 mols of the desired acid fluoride 1a. In a sense, this process can be called self-multiplication of a perfluorinated acid fluoride from a non-fluorinated alcohol.