The technique of ionic self-assembly (ISA), on the basis of electrostatic interactions, is a powerful tool to create new material nanostructures and chemical objects due to its advantages of facility, reliability, cost saving, flexibility, and universality. It has attracted great attention because of its promising applications in catalysis, drug delivery, and molecular detection. This review focuses on recent advances in the construction of self-assemblies with different morphologies on the basis of ISA strategy and its applications. The ISA method provides an opportunity to generate complex and hierarchical assemblies with tunable properties, which is regarded as a very promising case of supramolecular chemistry.