The self-assembly of amphiphilic calix[4]arenes with either a carboxylic acid or a trimethyl ammonium head group and different alkyl chains in aqueous solution was investigated. The carboxylated calixarene forms vesicles in dilute solution and stable monolayers on water. In contrast, the ammonium head group provides high water solubility with no observed aggregation. At high concentrations, all calixarene amphiphiles form lyotropic liquid crystals.