Bis(2,2,3,3,4,4,5,5,6,6,7,7-dodecafluoroheptyl) dipropargylmalonate (DFHDPM) and 4,4-methyl-[(tert-butyldimethylsilyl)oxy]-1,6-heptadiyne (MSHDY) were polymerized by MoCl5- and WCl6-based catalysts to give new polymers. A high polymer yield was obtained in the presence of MoCl5-based catalyst. Both polymers were amorphous violet solids, dissolved in common organic solvents, and their maximum number-average molecular weights reached ca. 1.0 x 10(5) and 5.8 X 10(3), respectively. The poly(DFHDPM) was film-forming, and its P(O2) and P(O2)/P(N2) values were 80 barrer and 2.8, respectively.