A metal-free visible-light-induced trifluoromethylation of Bunte salts of α-bromoketones/alkyl bromide/benzyl bromides/functionalized allyl (Baylis-Hillman) bromides has been accomplished using Langlois' reagent in the presence of inexpensive eosin Y as a photocatalyst to form the privileged trifluoromethylthiolated synthons. The method is straightforward, operationally simple, and endowed with broad substrate scope and good functional group tolerance.