A new copper-catalyzed three-component oxidative 1,2-trifluoromethylarylation of styrenes with NaSO₂CF₃ and indoles involving aryl C–H bond functionalization is described. This reaction is initiated by single electron transfer upon utilizing TBPB as an oxidant, thus enabling introduction of a CF₃ group and an aryl group into the CC bond of alkenes in a single step. This method represents a highly atom and step-economical access to various CF₃-substituted 1,1-diarylalkane derivatives in moderate to good yields with good functional group compatibility.