Leveraging α-fluoroalkyl or fluorobenzyl radicals to introduce fluorinated motifs allows for the rapid preparation of fluorine-containing building blocks. Herein, we report the generation of α-fluoroalkyl or fluorobenzyl radicals from readily available α-fluorocarboxylic acids under mild reaction conditions and their utilization in the Giese-type addition on Michael acceptors and dehydroamino acids, resulting in the preparation of mono- and difluorinated Michael addition adducts and unnatural fluorinated amino acids.