A new soluble polyamine with main chain perylene units is synthesized and subsequently converted into cationic or zwitterionic polyelectrolytes. The optical properties of the monomer 1,6,7,12-tetrakis(4-tert-butylphenoxy)-3,4,9,10-tetra(bromomethyl)perylene and the resulting polymers have been studied with special attention to ongoing de/aggregation processes. UVVis and PL spectra of the polymers show a distinct concentration and solvent dependency of the optical properties. In contrast to the corresponding monomer complete deaggregation did not occur for the polymers. The environment-sensitive optical properties should allow applications as sensor materials. The perylene-containing polyelectrolytes may be applied in orthogonal processing schemes toward multilayer electronic devices.