New ionic liquids have been synthesized by esterification of cyclohexanol with bromoacetic acid or chloroacetic acid to form cyclohexyl-2-bromoacetate or cyclohexyl-2-chloroacetate. The bromoacetate/chloroacetate on quaternization with heterocyclic bases (pyridine or 2-methylpyridine or 3-methylpyridine or 4-methylpyridine or N-methylimidazole) gave the respective ionic liquids. One of the ionic liquids has been subjected to ion exchange with potassium hexafluorophosphate, potassium trifluoromethanesulfonate, and sodium tetrafluoroborate to get their respective hydrophobic ionic liquids by the exchange of anions. To confirm the exchange of anions, these ionic liquids have been crystallized from acetone and their structures have been established with single crystal X-ray diffraction studies. All the ionic liquids have been found to possess good surface properties and are thermally stable up to a temperature of more than 473.15 K.