Radical initiation for the perfluoroalkylation reaction of sulfides has been performed using the complex [(TMEDA)I·I₃] and visible light. This methodology bypasses the use of metal(organo)catalysts where the complex [(TMEDA)I·I₃] acts as a good electron donor/reductant radical initiating agent. Biologically relevant sulfides are easily substituted with R_F moieties employing a mild and environmentally benign radical strategy starting from readily available R_FI.