Interpolyelectrolyte complexes (IPECs) were obtained from linear polyanion poly (2-acrylamido-2-methylpropanesulfonic acid) (pAMPS) and comb-like polycation poly(11-acryloyloxyundecyltrimethylammonium) bromide (pAUTA-Br) using different strategies comprising of mixing polyelectrolyte solutions in homogeneous and heterogeneous conditions and the polymerization of ionic monomer in the presence of opposite-charged polyelectrolyte. The supramolecular structure of IPEC in a solid state was studied by SAXD. The hexagonal or cubic order was revealed by IPEC obtained in different conditions. The lattice unit cell size appeared to be dependent on the solvent thermodynamic quality of the used polymers. These structures are pre-formed in solutions of comb-like self-organized components and fixed in a solid state in the course of kinetically driven IPEC formation.