A cationic surfactant and different anionic copolymers randomly grafted with side chains of ethylene oxide were used to prepare stoichiometric complex salts. Variations in the length or proportion of side chains were shown to be responsible for affecting the surfactant phase behavior in water, resulting in the observation of a number of structures characterized by small angle X-ray scattering measurements, including a hierarchical micellar system and different liquid-crystalline phases. Additionally, although aqueous mixtures of stoichiometric complex salts usually phase separate, the presence of a sufficiently high weight fraction of ethylene oxide side chains can enhance the solubility of the complex salt aggregates in water over a wide range of concentration. Moreover, a dispersion of an isotropic concentrated solution of complex salts is formed at higher temperatures in a reversible process. In summary, this study proves the importance of the polyion structure for tuning the properties of systems of complex salts.