The most commonly studied classes of ionic liquids (ILs) comprise relatively large and asymmetric heterocyclic cations (e.g., diakylimidazolium or N-alkylpyridinium) in combination with any of a wide variety of inorganic (e.g., BF4-, Cl-) or organic (e.g., bis[(trifluoromethyl- sulfonyl)imide], Tf2N-) anions. Recently it has been shown that ILs can also be formed by complexation reactions of metal cations (e.g., Li+, as its Tf2N- salt) with various neutral ligands (e.g., cyclohexano-15-crown-5 or alkylamines). Because the upper limit of the useful temperature range of any IL is governed by its thermal stability, and because the thermal stability of a neutral ligand (i.e., its propensity to either volatilize or decompose) is of obvious importance in determining that of an IL prepared from it, a systematic examination of the thermal properties of a series of macrocyclic polyethers of potential utility in the synthesis of new ILs has been undertaken. The results show that the temperature corresponding to the onset of mass loss upon heating (i.e., evaporation and/or decomposition) varies with the ring size, substitution, nature of the donor atoms, and stereochemistry of the macrocycle, but is most strongly influenced by the molecular weight and aromatic content of the compound.