After having demonstrated the general efficiency and robustness of the proposed protocol for the unprecedented direct and straightforward access to fluorinated hexestrol derivatives, we turned our focus to develop a similar strategy towards the selective hydrotrifluoromethylation of styrenes. This strategy relies on the working hypothesis that selective reduction of the benzylic radical generated by addition of trifluoromethyl radical to styrene should be a crucial step to avoid the dimerization of the formed intermediate. It has been shown recently that the difunctionalization of styrenes derivatives could be performed with PC2 (4CzIPN) in DMSO through the generation of benzylic anion from its corresponding benzylic silanes derivatives. In this context, the reduction of the radical intermediate (intermediate A on figure 3, vide infra) should be even more accessible thermodynamically given the electron withdrawing nature of the trifluoromethyl group, yielding a benzylic anion that after protonation should afford the desired hydrotrifluoromethylation products, avoiding the use of external additive (HAT donor). To our satisfaction, we were able to confirm this working hypothesis when the reaction was performed using DMSO as a solvent instead of MeCN. Under these conditions, still using PC1 as a photocatalyst, 3ea was obtained in 40% yield. After a quick optimization it turned out that compound 3ea could be obtained with a better yield of 55% by using PC2 (2 mol%) with an excess of the Langlois reagent (2 equiv.) in DMSO and longer reaction times.