Four ionic liquids (ILs) based on the bis(trifluoromethanesulfonyl)imide (NTf 2) anion were synthesized and characterized concerning their thermal stability, the occurrence of low temperature phase transitions and their volatility. All these physical quantities are highly important for possible applications. Both monocationic and dicationic ILs were considered. All ILs exhibit thermal stability exceeding 350 • C, an extremely high value, due to the presence of the NTf 2 anion. Monocationic ILs can undergo crystallization, and they melt at 1 and 38 • C. On the contrary, dicationic ILs containing large positively charged ions display only a glass transition around −40 • C, without any crystallization or melting process; this fact is particularly important in view of the possibly low temperature applications of the dication ILs. The vapor pressure, p v , of the four ILs was measured by isothermal thermogravimetry in the temperature range between 250 and 325 • C; the lowest values of p v were obtained for the two dicationic liquids, suggesting that they are particularly well suited for high temperature applications. The vaporization enthalpy was calculated through the Clausius-Clapeyron equation and was found in the range between ~140 and ~180 kJ/mol depending on the specific IL.