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A new kind of catalyst WOBr_4,which can be used in the polymerization ofphenylacetylene(PhA),has been synthesized.The obtained polyphenyl(?)cetylene(PPhA)using WOBr_4 as catalyst is soluble、fusible、with brown-red colour and has 1831(Mn).The analysis of the stucture of PPhA shows that the polymer has cis-transoidalstructure,therefore,the reaction mechanism is via complex catalysis.