AbstractEven though mixtures of polyelectrolytes and surfactants are used in a variety of technologies, little is known about the solid state properties of complexes formed by the two components. Recently reported methods for preparing polyelectrolytesurfactant complexes and their solid‐state structure will be described in the context of the self‐assembly behavior of the source surfactant molecules. This facile process offers the opportunity of producing a variety of new materials with applications that may range from switchable, permselective biological membranes to fluorinated materials with non‐wetting properties. In the form of a solid‐state complex, remarkably diverse mechanical properties ranging from elastomers to crystalline solids can easily be achieved. This review discusses the growing quantity of research in this new field, and in particular, the fabrication of such complexes in the form of processable self‐doped conducting polymers is