Our group recently started a new research program aiming to use organic photocatalysts for the fluorination/fluoroalkylkation of organic molecules. As a new step forward, we demonstrate herein that cyanoarenes are efficient organophotocatalysts to achieve the unprecedented synthesis of fluoroalkylated hexestrol derivatives or the hydrofluoroalkylation of styrenes depending on the solvent choice. Indeed, we show herein that solvent can directly impact the reaction mechanism and drives it either towards the reduction or dimerization process. Furthermore, we demonstrate that our system could also be further exploited in other types of radical styrenes substitution, including carboxylative trifluoromethylation and radical-radical cross coupling with cyanopyridine, enabling unprecedented direct access to complex molecular structures.