The photoinduced radical hydroperfluoroalkylation of unsaturated carboxylic acids using TTMSS as a H-donor was successfully developed. The stereoselective reaction using Oppolzer's camphorsultum was also achieved to give high stereoselectivity. The reaction was also effective for N-phthalimide-dehydroamino acid and the product was easily converted to the corresponding amino acid and a peptide derivative.