AbstractHerein 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.