We report the unprecedented use of PhPh-N-(SCF3)(CF3) as an efficient reagent for the formation of C-SCF3 bond under photoredox conditions. Here, we demonstrate that organophotocatalyst could be used in conjunction with bromine as an activator or in the presence of a HAT catalyst for the synthesis of vinyl-SCF3 and benzoyl-SCF3. Moreover, preliminary mechanistic investigations including EPR spectroscopy and cyclic voltammetry allowed us to identify key radical intermediates involved in the reaction mechanisms.