Abstract: A kind of phenylethynylpendentdecorated conjugated polymer, consisting of alternating fluorene and triphenylamine gorups, poly(9,9-dioctyl)2,7-fluoreneco-N-4-phenylethenyl-4,4'-tripheny-lamine(PFT-PE), was successfully synthesized via Suzuki coupling reaction. The chemical structure of PFTPE was verified by NMR and FTIR analyses. The polymer is highly soluble in common organic solvents, and exhibits good filmforming ability and thermal stability. The optical bandgap of this polymer is 2.82 eV, as deduced by its absorption onset. The PL spectrum of PFT-PE′s film showed substantial redshift and broadening as relative to that of its THF solution, indicating the presence of intermolecular aggregation in solid state. The highest occupied molecular orbital (HOMO) level of PFT-PE is about -5.39 eV, as calculated by the oxidation onset of its CV curve. The highly reversible oxidation process indicates the good electrochemical stability PFTPE possesses. PFT-PE can be thermally cured without the addition of any initiator due to the substitution of phenylethynyl pendant.