Polyphenylenes (PPs) with NH2 Side groups, namely, PFluNH(2) and PPhNH2, were synthesized by the Pd-complex-catalyzed reaction of 2,5-dibromoaniline with 9,9-dihexylfluorene-2,7-diboronic 2 and acid bis(1,3-propanediol) ester and 2,6-dioctyloxybenzene-1,4-diboronic acid. The reaction of PFluNH(2) PPhNH2 With 1-alkyl-1'-(2,4-dinitrophenyl)-4,4'-bipyridinium dichloride (alkyl = ethyl and n-hexyl) eliminated 24-dinitroaniline to yield PPs with viologen (1,1'-disubstituted 4,4'-bipyridinium dications) side groups, namely, PFluBPyHex, PFluBPyEt, and PPhBPyEt. The UV-vis spectra of PFluBPyHex, PFluBPyEt, and PPhBPyEt showed absorptions due to the viologen radical cation that was formed under nitrogen by the electron transfer from the polymer backbone to the viologen moiety. In contrast to photo luminescent PFluNH(2) and PPhNH2, PFluBPyHex, PFluBPyEt, and PPhBPyEt showed no photoluminescence because the viologen contained within them acted as it quencher. The ESR spectra of PFluBPyEt and PPhBPyEt confirmed the generation of the viologen radical. Cyclic voltammetry measurements suggested that an electrochemical reduction Of the viologen moiety and oxidation of the polymer backbone within PFluBPyEt and PPhBPyEt. Furthermore, this reaction was accompanied by electrochromism. The electric conductivities (sigma) of the pellets molded from PFluBPyEt and PPhBPyEt were 6.4 x 10(-6) and 1.1 x 10(-6) S cm(-1), respectively; these sigma Values were higher than those of PFluNH(2) and PPhNH2 (sigma < 10(-8) S cm(-1), respectively) due to the self-doping in PFluBPyEt and PPhBPyEt.