A novel phenylacetylene derivative containing a pyrene group was synthesized and polymerized with various Rh complex catalysts. The obtained polymers were soluble in common organic solvents such as chloroform and THF. The Mw and Mw/Mn were estimated as ca. 12000–18000 and 1.3–1.7 respectively, and the polymer yields were estimated as around 57–72%. The characteristic absorptions of ≡C–H (3200 cm−1) and C≡C (2100 cm−1) stretchings seen in the monomer spectra have completely disappeared in the polymer spectra from IR spectrum. 1H NMR analysis confirmed that the acetylene triple bonds transformed to polyene double bonds. These polymers were found to be thermally stable based on TGA data. The synthesized polymers exhibited blue fluorescence. The fluorescence quantum yield in solution was high at 0.37–0.41. Furthermore, the obtained polymer had a long fluorescence lifetime.