Tetrasubstituted trifluoromethylthiolated alkenes can be accomplished directly through the chlorotrifluoromethylthiolation of sulfur ylides utilizing nucleophilic halide reagent and electrophilic SCF3 reagent. This cascade reaction is mild, highly practical, easy to manipulate, uses catalyst-free conditions, and demonstrates a wide substrate range with excellent functional group tolerance, furnishing E-selective products in good to high yields. The synthetic utility of this approach is documented through gram-scale preparation and late-stage modification of pharmaceutically relevant compounds, making it suitable for drug discovery.