In summary we demonstrated that cyanoarenes are effective organophotocatalysts for the unprecedented selective and straightforward synthesis of hexestrol derivatives by using Langlois reagents and its derivatives in conjunction with styrenes. Furthermore, we were able to demonstrate that subtle variations of the initial reaction conditions, make it possible to drive its evolution towards hydrotrifluoromethylation of styrenes, which proceeds smoothly without the need of hydrogen atom donor. Our system was also efficient for the carboxylation of CO2 as well as a three component difunctionalization of styrene through radical-radical cross coupling process. Mechanistic investigation including EPR spectroscopy, luminescence as well as isotope labelling experiments allows us to propose plausible mechanisms for those different reactions, which, depending of the solvent used may proceed through a radical or anionic intermediate species.