New poly(diphenylacetylene)s with alkoxy and fluoroalkyl groups as electron-donating and electron-withdrawing groups, respectively were synthesized by using a WCl6-n-Ph4Sn catalyst. The polymer solutions emitted strong, bluish-green lights when photo-excited. The polymers that contained the electron-donating alkoxy groups showed longer fluorescence-maximum peaks when compared to the polymers that contained the electron-withdrawing fluoroalkyl. groups. However, such an effect of the substituent on the absorption property was not clearly seen. The emission bands of the solid films did not show any significant red shift, relative to that of the dilute solution.