The reaction mechanism of atom-transfer radical addition (ATRA) reactions of perfluoroalkyl iodides with styrene using a Cu(I) photoredox catalyst was analyzed using density functional theory calculations. From among four previously mentioned mechanisms, the ligand-transfer mechanism (ligand abstraction by the radical intermediate) was shown to be most plausible. It was also suggested that the ATRA product would also be reduced by the photoexcited Cu(I) complex.