Microwave heating offers a lot of advantages compared to conventional heating methods in the chemical reactions field due to its positive effects on reaction time and selectivity. Dielectric properties, and in particular permittivity, of substances and mixtures, are important for the optimization of microwave heating processes; notwithstanding this, specific databases are poor and far from being complete, and in the scientific literature very little data regarding these properties can be found. In this work, impedance measurements were carried out using a specially designed system to get the real and imaginary parts of the dielectric constant. The apparatus was tested in the estimation of permittivity of water−ethanol and water−NaCl mixtures, varying their composition to obtain a wide range of permittivity values. The results were compared to literature data and fitted with available literature models to verify the correspondence between them, finding that permittivity dependence on mixture composition can be effectively described by the models.