Novel pi-conjugated polymers 10a-c having the phosphole ring were prepared by PdCl2(PPh3)(2)/CuI catalyzed coupling of 1-phenyl-2,5-bis(p-bromophenyl)phosphole 8 with fluorine-substituted diethynylbenzene 9a-c. The obtained polymers 10a-c were regio-regulated with the 2,5-substituted phosphole ring in the polymer main chain, and characterized by H-1, P-31 NMR, and FTIR. Polymers 10a-c were found to be an extended pi-conjugated system according to the results of UV-Vis absorption spectra. In the fluorescence emission spectra of 10a-c, moderate emission peaks were observed in the visible blue to green region.