AbstractA 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. UV–Vis 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.