We report the highly regioselective cyclotrimerization of the 1-perfluoroalkylenynes in the presenceof Ni(PPh3)4. The substituent effects on the reactivity of the enynes were investigated. We alsosucceeded in the nickel-catalyzed cocyclization of the 1-perfluoroalkylenynes with (trimethylsilyl)acetylene. The possible structures of the intermediates of the cyclotrimerization and the reasonsfor the observed high regioselectivity were discussed.