Multilayer structures of an optically active ionic polymer complex, which are formed by poly(1,1-phenyleneethynylenecarboxylic acid) and dimethylditetradecylammonium bromide, were prepared. The complex as bulk material was investigated by small-angle X-ray scattering and found to be lamellar in structure with a repeat unit of 3.2 nm. This mesomorphous structure consists df alternating ionic layers (1.3 nm) and nonionic layers (1.9 nm) with periodic undulations of a hexagonal symmetry and a maximum-to-maximum distance of 7.5 nm. The positions of the undulations in adjacent layers are not correlated; this results in typical asymmetric random-layer peak profiles. By contrast, the lamellae of thin complex films (the film thicknesses were in the range of 14-140 nm) show no undulations. X-ray reflectivity and atomic force microscopy (AFM) were used for the film characterization. As revealed by AFM the multilayer films show dewetting instabilities at elevated temperatures. Symmetric complex droplets are the final stage of the dewetting process. The absorptive and emissive behaviors of complex solutions and complex films mere examined by W-vis and fluorescence spectroscopy. It was shown that the supramolecular structuring of the complex has a substantial influence on the optical properties.