Poly(9,9-dipropargylfluorenylene-phenylene) was prepared by cross-coupling condensation, known as the Heck reaction of 9,9-dipropargylfluorene (DPF) and 1,4-diiodobenzene in high yield. The polymer structure was identified by various spectroscopic methods such as IR, (1)H-, (13)C NMR, UV-visible spectroscopies. The acetylenic units in the polymer main chain were found to be thermal intermolecularly crosslinked in the range of 147-256 degrees C. The photoluminescence of the polymer in chloroform solution appeared at 408 nm, which corresponds to a photon energy of 3.04 eV.