The properties and characteristics of calix[n]arenes are described, as well as their capacity to form amphiphilic assemblies by means of the design of synthetic macrocycles with a hydrophilic head and a hydrophobic tail. Their interaction with various substances of interest in pharmacy, engineering, and medicine is also described. In particular, the role of the calix[n]arenes in the detection of dopamine, the design of vesicles and liposomes employed in the manufacture of systems of controlled release drugs used in the treatment of cancer, and their role in improving the solubility of testosterone and anthelmintic drugs and the biocompatibility of biomaterials useful for the manufacture of synthetic organs is emphasized. The versatility of these macrocycles, able to vary in size, shape, functional groups, and hydrophobicity and to recognize various biomolecules and molecules with biological activity without causing cytotoxicity is highlighted.