The use of ionic liquids (ILs) as alternatives to common molecular solvents is rapidly expanding.[1] For assessing their solvent behavior, the polarity is of key interest. [2][3][4] Polarity describes the solvation capability, but different experiments probe different facets. A key quantity for gauging the polarity is the relative dielectric permittivity, e S ('dielectric constant'). The electrical conductivity of ILs renders conventional measurements of e S impossible, but microwave dielectric spectroscopy [5][6][7][8][9][10] allows to separate the dielectric and conductive responses, which enables the determination of e S . The results for widely used ILs, mainly 1,3-dialkylimidazolium salts, indicate remarkable features. First, the values of e S = 10-15 at 25 8C vary little compared to the wide range of values covered by molecular solvents. This insensitivity to the chemical nature of the ions contrasts the behavior of many other properties of ILs, which can be varied over wide ranges. Second, e S is substantially lower than observed for common polar solvents, which contradicts the expectation that a charged system forms an environment of high polarity. One can think of many scenarios where ILs of higher dielectric constant are desirable.There is the pressing question to which extent these features are generic for ILs. In molecular liquids, high dielectric constants are often found in hydrogen-bonded structures, where strong orientational correlations between dipoles can enhance dielectric polarization. [11,12] It seems therefore worthwhile to study the dielectric behavior of "protic ionic liquids". Protic ILs are formed by a combination of a Brønsted acid and a Brønsted base. Their properties and applications have recently been reviewed.[13] A well-known representative is ethylammonium nitrate, [14] which can form an extended hydrogenbonded network.[13] Its dielectric constant of e S = 26.2 at 25 8C [5] is indeed higher than those of common aprotic ILs. A high polarity of protic ILs is also indicated by other probes, for example based on solvatochromic shifts.[13]For conductive liquids, measurement of e S resorts to the determination of the frequency-dependent dielectric dispersion curve e 0 ðnÞ in the microwave regime, here 30 MHz n 20 GHz, where the dielectric response can be separated from the conductance response.[6] e S is given by the zero-frequency limit of the dispersion curve [Eq. (1)]Although the electrical conductance imposes a low-frequency limit for useful experiments, the optimized experiments [6] cover a sufficiently large segment of e 0 ðnÞ for an accurate extrapolation of e S by fits to well-established target functions. [5][6][7][8][9][10][11] Figure 1 shows dispersion curves for two representative proticILs. Table 1 lists e S values for six protic ILs. The results vitiate the impression from earlier studies that dielectric constants fall into a narrow range of fairly low values. Obviously, the hydrogen-bonded structure of a protic IL enhances the dielectric polarization. For the alkylammoni...