The effect of phase transitions in the solutions of the complexes of surfactants and oppositely charged polyelectrolytes of different chemical natures on the molecular mobility of the surfactant ions inside the intracomplex micelles was studied by the spin probe method. It was found that, irrespective of the fact whether the solutions of the polyelectrolyte–surfactant complexes are true solutions, colloidal dispersions, or thixotropic gels, the molecular mobility of the surfactant ions inside the complex micelles and, consequently, the local structure of the intracomplex micelles, remain unchanged upon both a change in the complex composition and transition of complexes from solution to the precipitate.