Polyphenylacetylenes were synthesized by [Rn(nbd)Cl]2 and WCl6／Ph4Sn catalyst systems in N2 at room temperature．Polymers with high yield and high molecular weight were obmined．Thdr structures were characterized by UV

IR

NMR and GPC

respectively．The fluorescence of the polymer solution with different concentration was investigated using variabh exci~tmn wavelength from UV to visible region．The relation between fluorescence and polymer structure Was studied．The results showed that the molecular chain structure has great influence on fluorescence of the polymers．The emitting peak wavelength of fluorescence for the polymer of high stereoregularity is independent of solution concentration and excitation wavelength．The emitting peak wavelength of fluorescence for the polymer with disordered molecular chain arrangement varies with changing the solution concentration and excitation wavelength

and different emission sites in molecular chains and loW emitting yield are shown．The measurement and analysis of fluorescence spectroscopy of polyphenylacetylenes may provide some useful information to judge the molecular chain arrangement in some conjugated polymers．