To get more insight on the reaction mechanism, we performed cyclic voltammetry studies. Herein, addition of one equivalent of sodium bromide shifted the potential of reagent I from -1.97 V (vs. Ag/Ag+) to -1.74 V. This shift confirms the requirement for bromide salt to be used for the reaction to proceed (see optimisation table) and could be associated to the formation of a new adduct . We suggest that the activation of reagent I with bromide anion could likely lead to the in situ formation of BrSCF3 as mentioned in previous studies reported by and Glorius. Based on the mechanism already proposed by Hopkinson and Glorius and our preliminary EPR and cyclic voltammetry investigations, we propose the following mechanism could take place under the reaction conditions. Activation of reagent I with bromide anion leads to the in situ formation of BrSCF3. The exited photocatalyst PC1 reduces this intermediate affording a radical anion that can deliver the key SCF3 radical intermediate. This radical then adds onto the styrene derivative to provide C-centred radical C as demonstrated by EPR. Finally, oxidation of intermediate C allows regenerating the active organophotocatalyst PC1 and a new cationic intermediate D that affords the desired product upon elimination. To further confirm the need for light, On/Off experiments were conducted and confirmed the stepwise mechanism involved in this transformation (see ESI for details) Scheme 5. Proposed mechanism for the synthesis of vinyl-SCF3 Afterwards, to further exploit the reactivity of reagent I, we decided to investigate the synthesis of benzoyl-SCF3 derivatives under organophotoredox conditions. Access to such compounds has already been demonstrated by reacting Munavalli's reagent and aldehydes under photochemical conditions. Indeed, while the Glorius 15 group reported a dual strategy using an iridium-based photocatalyst in conjunction with catalytic amount of sodium benzoate under blue LED König and co-workers employed decatungstate as photocatalyst under 385 nm LED irradiation. Inspired by these studies, we reacted reagent I and aldehyde 3a in MeCN in the presence of 5 mol% of organophotocatalyst PC1 and 5 mol% of sodium benzoate (PhCOONa) at room temperature under blue LED irradiation. Under these conditions, desired product 4a was obtained in an excellent yield of 97% (Scheme 6). Then, we investigated the scope of the reaction by functionalising several aryl aldehydes bearing different functional groups. Pleasingly, both electron donating and electron-withdrawing groups were tolerated under the reaction conditions affording the desired products in excellent yield (up to 91%, compounds 4b-4f, Scheme 6). In contrast, using 2-naphthaldeyde provided the desired product in a low yield of 22% (compounds 4g, Scheme 6). Interestingly chlorine or bromine atoms on the aldehyde starting material were tolerated and the desired products were obtained in 76% and 85%, respectively (products 4h and 4i, Scheme 6). Finally, an excellent yield of 90% was obtained when starting with benzothiophene derivatives (compound 4j, Scheme 6). Scheme 6. Scope for the synthesis of benzoyl-SCF3 [a] Reactions were performed with 1 (0.2 mmol, 1 equiv.), reagent I (0.24 mmol, 1.2 equiv), NaBr (0.2 mmol, 1 equiv.), PC1 (5 mol %) and MeCN (2 mL). The reaction mixture was stirred under blue LED irradiation for 16 hours unless otherwise noted. Yield of isolated products.