A series of conjugated polyelectrolytes (CPEs) based on an electron-deficient polybenzotriazole backbone with various pendant ionic functionalized side chains were synthesized directly from the corresponding ionic monomers. Of particular interest was to use the different chemical structures to understand how the optical features are influenced by the ionic side chains. We found that interchain aggregation is favored in low dielectric constant solvents for cationic CPEs. Moreover, aggregated species absorb at longer wavelengths and exhibit higher fluorescence quantum yields.