This feature article is intended to describe a route from Langmuir monolayers as the most suitable and, well-defined models to polyelectrolyte multilayers. The latter are structurally controlled not with angstrom but with nanometer precision; however, they are very modular with regard to building blocks and function and are robust, therefore promising many diverse applications. There have been many methods developed to structurally characterize Langmuir monolayers; therefore, they serve as models in membrane biophysics and materials science as well as in general physics as two-dimensional model systems. Many of these methods as well as ideas to control, interfaces could be taken over to study polyelectrolyte multilayers with their extended internal interfaces. Finally, as an outlook we try to sketch various aspects to transit toward systems with higher structural hierarchy, enabling the coupling of different functions and arriving at responsive three-dimensional systems.