Abstract The nickel‐mediated [3+2] cycloaddition of 2‐trifluoromethyl‐1‐alkenes with alkynes afforded fluorine‐containing multi‐substituted cyclopentadienes in a regioselective manner. This reaction involves the consecutive two CF bond cleavage of a trifluoromethyl or a pentafluoroethyl group through β‐fluorine elimination.