The technique of ionic self-assembly i.e., the coupling if structurally different building blocks of electrostatic interactions, a powerful tool to create new material nanostructures and chemical objects, is reviewed. The excellent availability of the starting products (charged tectonic units) and the simplicity of synthesis, by neat addition and cooperative stoichiometric precipitation with high purity, allow the recombinatorial synthesis of a whole range of functional materials and hybrids with interesting and versatile functions. Diverse combinations between polyelectrolytes, surfactants, clusters, and extended rigid organic scaffolds are discussed in detail, and the underlying principles of nanostructure formation are illustrated.