Supramolecular assemblies of amphiphiles include monolayers, bilayers, multilayers, as well as nonlamellar structures. The recent introduction of methods to polymerize supramolecular assemblies has increased the range of chemical and physical stabilities of these new materials. Polymerized supramolecular assemblies offer opportunities to prepare new materials for both biological and materials sciences. Polymerization has proven a valuable probe of the similarities of molecular order within bilayers and multilayers, and to examine the transformation of the first into the latter. It is also possible to initiate the transformation from lamellar to nonlamellar assemblies via polymerization induced processes within the assembly. Examples of each of these types of supramolecular conversions are described.