The neat phases of a series of quaternary ammonium halides based on trioctadecylamine have been investigated by optical microscopy, differential scanning calorimetry, and H NMR spectroscopy. Phase behaviour depends primarily on the structure of the fourth substituent on nitrogen and the thermal history of the samples. For instance, the iodide salts with methyl, ethyl, or propyl as the fourth substituent form enantiotropic nematic phases, while those with a proton or a longer alkyl substituent exhibit complex phase behaviour that does not include a liquid crystalline phase. Possible reasons are advanced for the unprecedented formation of nematic phases.