Synchrotron X-ray scattering was used for the structural investigation of complexes between anionic polyelectrolytes and cetylpyridinium chloride (CPC). According to the Bragg peaks, different types of ordering are proposed. Cetylpyridinium chloride in con;junction with carrageenan forms bilayers connecting rigid polysaccharide chains. In the presence of poly(styrenesulfonate), several micelles are bound to one chain. They appear rather small in size due to specific interactions with this polyion. In poly(acrylate)/CPC and poly(methacrylate)/CPC solutions, a cubic structure is indicated.