Trifluoromethyl phenyl sulfone is traditionally a nucleophilic trifluoromethylating agent. Herein, we report the first example of the use of trifluoromethyl phenyl sulfone as a trifluoromethyl radical precursor. Arylthiolate anions can form electron donor–acceptor (EDA) complexes with trifluoromethyl phenyl sulfone, which can undergo an intramolecular single electron transfer (SET) reaction under visible light irradiation, thus realizing the S-trifluoromethylation of thiophenols under photoredox catalyst-free conditions. Similar S-perfluoroethylation and S-perfluoro-iso-propylation of thiophenols are also achieved using the corresponding perfluoroalkyl phenyl sulfones.