α-Fluoro-β,γ-unsaturated esters are synthetized in high yields by photodeconjugation of the α-fluoro-α,β-unsaturated isomers in the presence of a base. In contrast to the α-bromo analogues, no homolytic cleavage of the carbon-halogen bond is observed during the irradiation. The reaction has been successfully applied to the enantioselective synthesis of optically active fluoroesters when conducted with a chiral protonating agent.