We started our study by investigating the direct access to fluoroalkylated hexestrol derivatives. To do so, we selected styrene 1e as model substrate in the presence of Langlois reagent (sodium trifluoromethanesulfinate, CF3SO2Na) as a cheap and easy to handle trifluoromethylating reagent. This latter exhibits an oxidation potential of 1.05 V (vs. SCE). In this context we selected PC1 with a reduction potential (Ered 1/2 (PC1/PC1˙-) of -1.59 which makes it able to oxidize the Langlois reagent under photoactivation conditions. The reaction was performed in MeCN as solvent upon blue LED irradiation at room temperature and the desired product was observed in an overall excellent yield of 95%. The reaction does not require the presence of any additives and gives rise, beside the meso form, to a pair of d,l enantiomers (with a ratio of 1:1.2). Although an excellent yield was already obtained in those native conditions, we decided to investigate the impact of different variations on the reaction outcome and to screen other organophotocatalysts. In a first serie of experiments, we therefore considered the effects of solvent variations. Only traces of the desired product were obtained when substituting MeCN with MeOH (10%, Table , entry 2) while no detectable formation of the target product was observed in toluene (Table , entry 3). Only DMF was also effective under our conditions since an excellent yield of 85% was reached (table 1, entry 4). Afterwards, other organophotocatalysts were tested. PC2 (4CzIPN) was to some extent also effective under our conditions although product formation yield dropped in this case to 75% (Table ). Surprisingly, Eosin Y was not effective and no product formation was observed (Table , entry 6). Sparr's organophotocatalysts which have shown similar reactivity to that of cyanoarenes derivatives were also investigated: in the present case PC4 allows to obtain the desired product in only 30% yield while higher efficiency was observed with PC5 affording a 60 % yield ( PC2 instead of PC1 75 6 PC3 instead of PC1