The mesomorphic properties of 15-membered azamacrocycles containing long hydrocarbon or highly fluorinated long chains have been explored along with those of their open precursors. The liquid crystalline behaviour is determined by the presence of different heteroatoms or long fluorinated chains and the substitution pattern of the aryl units of the sulphonamides. The presence of highly fluorinated long chains in the para position with regard to the sulphonamide group was found to favour the formation of smectic mesophases with wide temperature ranges. All of the mesophases were studied by polarizing optical microscopy and differential scanning calorimetry. © 2007 Taylor & Francis.