A variety of vinylic bromides and iodides undergo smooth trifluoromethylation and pentafluoroethylation with RfH-derived CuRf (Rf = CF3, C2F5) to give the corresponding fluoroalkylated olefins. These reactions employing the low-cost CuRfreagents occur in high yield with excellent chemo- and stereoselectivity under mild conditions (23–80 °C). Crystal structures of one trifluoromethyl and one pentafluoroethyl derivative have been determined.