Hydrated, but water-insoluble, “complex salts” (CS) composed of alkyltrimethylammonium surfactant ions with polyacrylate counterions are known to exhibit a rich phase behavior in bulk mixtures with water and have recently been shown to act as water-responsive surface coatings. Here it is shown, by SAXS measurements, that surface coatings of CS also respond to various added solutes in a surrounding aqueous solution, by altering their liquid crystalline structure. The obtained results provide new information on the phase behavior of CS in contact with water and aqueous solutions. Solutes such as acids, salts, excess ionic surfactant, or water-soluble polymers act on the CS by altering the polyion charge density, screening the electrostatic interaction, changing the curvature of the surfactant aggregate, or increasing the osmotic pressuring in the surrounding solution, all of which may result in a phase transition in the film. In water, all studied CS surface coatings had a micellar cubic structure, which could change to 2D hexagonal, HCP, or disordered micellar structure, depending on the identity of the CS and the identity and concentration of the added solute. For some systems, even dissolved CO2 from the ambient air was sufficient to induce a structural change in the film. Especially the films containing the long polyions remained intact even for large concentrations of solutes in the contacting solutions, and extensive washing in water resulted, in most cases, in films with the “original” structure found in water.