The Suzuki (for O1-O3) and Stille (for O4) coupling polymerization of 2-(phenylazo)imidazole bearing the benzyl protecting group at the 1-position gave conjugated oligomers. The transformation from the neutral imidazole in the conjugated oligomer O2, consisted of the alternating 2,5-didecyl-1,4-phenylene unit, to the cationic imidazolium salt O2S was performed. Depending on the chemical structure of coupling partners, the absorption maximum of conjugated oligomers showed red shift or blue shift from that of the model compound M with the benzene ring at the 4,5-positions. The absorption maximum wavelength of the cationic conjugated oligomer O2S showed a blue shift from that of the neutral conjugated oligomer O2. The trans-to-cis photoisomerization of the azoimidazole unit in conjugated oligomers was observed by irradiating the light at 436 nm, and the conversion degree to the cis structure had a rough correlation with the maximum absorption wavelength of materials. The trans-to-cis photoisomerization in the film state was sluggish. On the other hand, the cis-to-trans thermal isomerization of the azoimidazole unit was confirmed and the absorbance returned to the initial state before the photoisomerization. The trans-to-cis photoisomerization of the cationic conjugated oligomer O2S required large energy, and the prolonged light irradiation might decompose the azoimidazole unit. (C) 2011 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 49: 4993-5000, 2011