In conclusion, we demonstrated that PhPh-N-(SCF3)(CF3) compound I could be used as a new efficient reagent for the construction of C-SCF3 bonds under mild organophotocatalysed conditions. We first demonstrated that the association of reagent I with bromide anion and styrene derivatives allows the formation vinyl-SCF3 compounds in moderated to excellent yields. Then, we reported that the association of this reaction with a HAT catalyst provides the formation of benzoyl-SCF3 compounds when using aldehydes as starting materials. EPR spectroscopy experiments allowed the detection of key radical intermediates and delivered precious preliminary information regarding the reaction mechanism. Further investigations using reagent I are currently conducted in our laboratory and will be reported in due course.