With the best conditions in hand, we investigated the scope of the reaction. We initially subjected several styrene derivatives to the optimized reaction conditions. Styrenes bearing electron donating groups were successfully trifluoromethylthiolated and the desired products were obtained in synthetically useful to excellent yields (compounds 2b and 2c). Moreover, halogenated motifs including chlorine and fluorine atoms were tolerated under the reaction conditions and the desired products 2d and 2e were obtained in 75% and 86% yields, respectively. Finally, dibenzo-annulene derivatives were successfully used as starting material and the corresponding vinyl-SCF3 products were obtained in moderate to very good yields (up to 71%, compounds 2g and 2f).