In a recent issue of the Journal of the American Chemical Society, Cornella and co-workers demonstrated a novel Bi-catalyzed C–H trifluoromethylation of (hetero)arenes by using CF3SO2Cl as the trifluoromethyl reagent under visible-light irradiation. This unique reaction mode also unveils the potential for the development of efficient catalytic redox processes by the main-group element.