Abstract: A perfluoroalkylene .alpha.,.omega.-diacetylene compound having a fluorocarbon chain of from 5 to about 20 carbon atoms between two acetylene end groups, and a method of forming same by first carrying out the addition reaction of a perfluoroalkylene diiodide having the formula I(CF.sub.2).sub.n I, where n is a whole number from 5 to about 20, inclusive, and trimethylsilyacetylene in the presence of a free radical catalyst to form (CH.sub.3).sub.3 SiIC.dbd.CH(CH.sub.2).sub.n CH.dbd.CISi(CH.sub.3).sub.3 ; subjecting the (CH.sub.3).sub.3 SiIC.dbd.CH(CF.sub.2).sub.n CH.dbd.CISi(CH.sub.3).sub.3 to dehydrohalogenation with DBU under dry conditions to obtain (CH.sub.3).sub.3 SiC.tbd.C(CF.sub.2).sub.n C .tbd.CSi(CH.sub.3).sub.3 ; and removing the silyl group from the latter compound with excess DBU or KF to yield HC.tbd.C(CF.sub.2).sub.n C.tbd.CH as the perfluoroalkylene .alpha.,.omega.-diacetylene compound. The HC.tbd.C(CF.sub.2).sub.n C.tbd.