Self-assembly provides a route for the formation of systems ordered at the molecular level. Ordered multilayers can be formed using selective ionic interactions. The incorporation of chromophores into these systems provides a method of building non-centrosymmetric films of interest for a variety of uses, from non-linear optics to piezoelectric or pyroelectric effects. This paper reports on the development of the above technique to build up multilayer films and details their characterization via a variety of spectroscopic techniques.