The polymerization of 3-ethynylphenol, phenylacetylene having hydroxy functionality, was carried out by tungsten and molybdenum-based transition metal catalysts. The polymerization proceeded to give a moderate yield of polymer. The effects on the mole ratio of monomer to catalyst (M/C), initial monomer concentration ((Mb), and the polymerization temperature for the polymerization of 3-ethynylphenol were investigated. The catalytic activity of W-based catalysts was found to be greater than that of Mo-based catalysts. The resulting polymers were brown or black powders and mostly insoluble in organic solvents. Structural analysis of the polymer by instrumental methods revealed the conjugated polymer backbone structure carrying hydroxyphenyl moieties. Thermal and morphological properties of the resulting poly(3-ethynylphenol) were also discussed.