We developed the copper-mediated synthesis of trifluorostyrene derivatives. beta-Fluorine elimination of a 2-aryl-1,1,2,2-tetrafluoroethylcopper complex, generated in situ from aryl-boronate, copper tert-butoxide, and 1,10-phenanthroline with tetrafluoroethylene (TFE) via carbocupration, was promoted by the addition of a Lewis acid. The present reaction system was applied to the one-pot synthesis of various trifluorostyrene derivatives, through the transmetalation carbocupration-beta-fluorine elimination sequence.