Fluorinated molecules play pivotal roles in several chemical areas ranging from life science to materials. In this context, the increased interest in accessing functionalized molecules bearing a fluorine atom favoured the development of very efficient methodologies for the incorporation of fluorinated motifs. 2 Among these fluorinated motifs, the SCF3 group has attracted considerable attention over the past decade. This group possesses unique physiochemical properties including high lipophilicity with a Hansch parameter value of 1.44. Thus, such a moiety facilitates transmembrane permeation of the molecules improving their bioavailability. In this regard, several new reagents including commercially available ones have been reported. Given the high interest in SCF3 motif in organofluorine chemistry, the synthesis of easily accessible new reagents is highly desirable. We have recently reported the robust and efficient one-pot synthesis of unprecedented N-(SCF3)(CF3) compounds from commercially available starting materials. Upon evaluating their stability, it turned out that compound I (Scheme 1) demonstrated excellent stability in water, organic solvents, and under different physiological conditions. However, this compound quickly degraded under basic conditions, raising the question of its ability to be a source of fluorinated motif. Thus, we disclose herein that PhPh-N-(SCF3)(CF3) can be used to forge C-SCF3 bond under mild visible light irradiation conditions by using an organophotocatalyst. To validate the use of reagent I in photochemical trifluoromethylthiolation of styrenes 10 we selected conditions reported by Hopkinson, Glorius and co-workers where the authors successfully reacted Munavalli's reagent with nBu4NBr to in-situ generate BrSCF3. We conducted the reaction between styrene 1a and reagent I in MeCN at room temperature under blue LED irradiation using cyanoarene 12 derivatives as organophotocatalyst instead of using the iridium-based photocatalyst employed by the Hopkinson and Glorius groups. To our delight, 2.5 mol% of PC1 (4CZIPN) furnished the desired vinyl-SCF3 product 2a in 50% yield (Table , entry 1). Encouraged by this first test, we evaluated other cynaoarene organophotocatalysts. The desired product was observed with PC2, PC3 and PC4 albeit with lower efficiency than with PC1 ). Afterwards, the use of other chloro and iodo ammonium salts also furnished desired product 2a but in only 30% yield (Table ). Using sodium bromide instead of tetra-butylammonium bromide afforded similar yield (Table ). Thus, due to its cost-effectiveness, NaBr was used for the rest of the optimisation. Then, the effect of solvent was studied. While DMF afforded desired product 2a in 40% (Table ), other solvents including toluene, ether, or DCM only provided marginal yields (Table , entries 9-11). Finally, increasing the photocatalyst loading to 5 mol% allows the formation of desired product 2a in an excellent 85% yield (Table , entries 12).