New phosphorous catanionic amphiphiles were easily prepared by an acid-base reaction between (alpha-hydroxyalkyl)-phosphinic or -phosphonic acid and cethyltrimethylammonium hydroxide. In this way, we obtained, in nearly quantitative yields, bicatenary phosphinates and bicatenary and tricatenary phosphonates. The aggregation properties of these new catanionic amphiphiles were investigated at low concentrations in water (ranging from 1 to 5 mM), focusing in particular on spontaneous formation of different aggregate morphologies (vesicles, ribbons, tubules). Light and electron microscopy was used to identify the aggregate morphology of the catanionic amphiphiles. Moreover, these catanionic amphiphiles were able to organize into ordered lyotropic mesophases in concentrated water solutions, visualized by optical polarizing microscopy. Finally, the phosphorous catanionic amphiphiles, without rigid cores, were unexpectedly found to show thermotropic liquid-crystalline behavior. The various thermotropic mesophases were characterized by the formation of optical textures. Rigidification by ionic interactions could promote the formation of these thermotropic mesophases.