Within the field of supramolecular materials and constructions, supra-amphiphiles (SAs) have arisen as a new area of research and application activity. To produce such constructs, non-covalent interactions are exploited for the fabrication of supramolecularly assembled amphiphiles that have the ability to undergo further assembly into micelles, vesicles or nanofibers. Here we provide an overview of the use of electrostatic interactions to produce the so-called electrostatic SAs (eSAs). We discuss the use of both low molecular weight small molecules and polymeric structures for the production of eSAs. We highlight switchability and orthogonal functionality in these eSAs, which is enabled through the exploitation of dynamic non-covalent interactions, and discuss application areas, especially in drug delivery. Promising areas earmarked for future exploration and application are discussed. A combination of covalent and non-covalent assembly strategies for materials synthesis is seen as a powerful tool to harness the potential of this exciting class of materials.