Herein we report a visible-light-induced trifluoromethylative difunctionalization of styrenes and phenylacetylenes using trifluoromethyl thianthrenium triflate (TT-CF3+OTf−). The transformation was enabled by the discovery of a photoactive catalytic EDA complex formed between carbazolyl dithiocarbamate and TT-CF3+OTf−. This three-component reactivity platform establishes a new paradigm for TT-CF3+OTf−, significantly expanding its repertoire of photochemically enabled trifluoromethylation reactions.