We report on a conjugated polyelectrolyte (CPE) based on fluorene repeat units, which forms a supramolecular complex with a zwitterion surfactant. The complex self‐assembles into multilamellar structures on solid substrates. The luminescence efficiency, low in the uncomplexed polymer, is strongly increased after complexation. This originates from the phase segregation between the aromatic backbone and ionic sides, reducing conformational defects and ionic dipole‐induced quenching.